Substituted phthalides and heterocyclic phthalides

ABSTRACT

Substituted phthalides and heterocyclic phthalides and derivatives thereof which are useful as herbicides are described.

This is a continuation of application Ser. No. 08/036,006, filed Mar.23, 1993, now abandoned, which is a continuation-in-part of applicationSer. No. 07/804,150, filed Dec. 6, 1991, now abandoned, which is acontinuation-in-part of application Ser. No. 07/633,592, filed Dec. 21,1990, now abandoned, which is a continuation-in-part of application Ser.No. 07/534,794, filed Jun. 7, 1990, now abandoned.

The present invention concerns substituted phthalides and heterocyclicphthalides and derivatives thereof, processes for their production,compositions containing them and their use in agriculture.

More particularly, the invention concerns compounds of formula I##STR1## wherein ring system A is selected from a) phenyl or naphthyl

b) pyridyl which may be fused by its (b) or (c) side to benzene

c) pyridyl-N-oxide or pyrazinyl-N-oxide

d) pyrimidinyl

e) pyrazinyl

f) 3- or 4- cinnolynyl or 2-quinoxalinyl, and

g) a five membered heteroaromatic ring comprising oxygen, sulphur ornitrogen as heteroatom(s) which ring may be fused to a benzene ring ormay comprise nitrogen as an additional heteroatom.

R is cyano, formyl, CX₁ X₂ X₃, a ketone forming group, a carboxyl groupwhich may be in the form of the free acid or in ester or salt form, athiocarboxyl group which may be in the form of the free acid or in esterform, a carbamoyl group or a mono- or di- substituted carbamoyl group,hydroxyalkyl, hydroxybenzyl, --CH═NOH, --CH═NO--lower alkyl, the group--CH₂ --O--C(O)-- which bridges adjacent carbon atoms in ring A, or aring C ##STR2## Y₁, Y₂ and Y₃ are attached to carbon atoms and areindependently hydrogen, halogen, hydroxy, alkyl, alkenyl, alkynyl,alkoxy, alkenyloxy, alkynyloxy, alkylsulfonyloxy, dialkylsulfamoyloxy,alkylsulfonyl, alkylsulfinyl, dialkylcarbamoyloxy, alkylthio,alkenylthio or alkynylthio each of which may in turn be substituted by 1to 6 halogen atoms; dialkoxymethyl, conjugated alkoxy, hydroxyalkyl,carboxyl, acyl, acylalkyl, acyloxy, acyloxyalkyl, trialkylsilyloxy,trialkylsilyl, cyano, nitro, amino or substituted amino, aminosulfonyl;cycloalkyl, aryl, aralkyl, aralkenyl, aralkynyl, aryloxy, aralkoxy,arylsulfonyl, arylsulfinyl, arylthio or aralkylthio, each of which maybe substituted by one to three substituents selected from halogen,alkyl, haloalkyl, alkoxy, haloalkoxy, nitro, cyano, alkylthio, acyl,amino or substituted amino; a group ##STR3## wherein R' is hydrogen,lower alkyl, or lower alkoxy; or Y₁ and R taken together on adjacentcarbon atoms form a bridge having the formula ##STR4## wherein E is adirect bond or a 1 to 3 membered linking group with elements selectedfrom methylene, substituted methylene, ##STR5## and oxygen. or Y₁ and Y₂taken together on adjacent carbon atoms form a 3- to 5-membered bridgecomprised of elements selected from methylene, substituted methylene,##STR6## each of W₁, W₂, W₃, W₄ and W₅ is independently CH, CR₃ ornitrogen; W₆ is NH, oxygen, sulfur, ##STR7##

Z is a 2- or 3-membered bridge comprised of elements selected frommethylene, substituted methylene, ##STR8##

R₁ and R₃ each is independently hydrogen; halogen; alkyl, alkenyl,alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkenylthio oralkynylthio, each of which may in turn be substituted by 1 to 6 halogenatoms; cycloalkyl, heterocycloalkoxy, aryloxy, aralkoxy or aralkylthioeach of which may be substituted by 1 to 3 substituents selected fromhalogen, alkyl, haloalkyl, alkoxy, haloalkoxy, nitro, cyano, alkylthio,acyl, amino or substituted amino; aminoxy; substituted aminoxy; iminoxy;substituted iminoxy; amino; substituted amino; amido; substituted amido;alkylsulfonylmethyl; cyano; nitro; or ##STR9## wherein Y₄ is hydrogen,lower alkyl, lower alkoxy, hydroxy or unsubstituted or substitutedphenyl.

R₄ is as defined for Y₁ except for hydrogen.

X and Y each is independently hydrogen, hydroxy, halogen, cyano, nitro,alkyl, alkoxy, alkoxycarbonyl, alkoxycarbonyloxy, hydroxyalkyl,haloalkyl, acyl, acyloxy, carbamoyl, carbamoyloxy, alkylthio,alkylsulfinyl, alkylsulfonyl or alkylsulfonyloxy; aryl, aryloxy,arylS(O)_(p), aralkyl, aralkoxy, aralkS(O)_(p), arylsulphonyloxy, eachof which may in turn be substituted by 1 to 3 substituents selected fromhalogen, alkyl, haloalkyl, alkoxy, haloalkoxy, nitro, cyano, alkylthio,acyl; amino, substituted amino or together represent ═O, ═S , ═NH,═NOR₁₂ or ═CR₁₃ R₁₄ ; or

X and R together may form a bridge having the formula --O--E--,##STR10## wherein the carbonyl is attached to A, E is defined above andR₂ represents hydrogen, hydroxy, alkyl, haloalkyl, alkoxyalkyl, alkoxy,aralkoxy, unsubstituted or substituted aryl, unsubstituted orsubstituted aralkyl or is as otherwise defined for R₇ hereinafter.

P is 0, 1 or 2.

X₁, X₂ and X₃ are independently hydrogen, hydroxy, alkoxy, alkylthio,hydroxyalkyl or hydroxybenzyl whereby at least one of X₁, X₂ and X₃ isother than hydrogen; or X₃ represents hydrogen and X₁ and X₂ togetherform a four or five membered bridge comprising elements selected from--O(CH₂)_(n),O--, ##STR11##

R₁₂ is hydrogen or alkyl,

R₁₃ and R₁₄ are independently hydrogen, alkyl or halogen,

m is one or two,

n' is two or three

with the proviso that when R is carboxyl in free ester or salt form andX and Y together are ═O one of rings A and B contains a hetero atom.

When R is a ketone forming group this is preferably ##STR12## wherein R"is alkyl, haloalkyl, alkoxyalkyl, alkenyl, alkynyl, unsubstituted orsubstituted aryl, unsubstituted or substituted aralkyl.

When R is a carboxyl or thiocarboxyl group in ester form it ispreferably of formula --COOR₅ or --COSR₅ wherein R₅ is alkyl, haloalkyl,alkoxyalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, unsubstitutedor substituted aryl, unsubstituted or substituted aralkyl, hydroxyalkyl,cycloalkyl, cyanoalkyl, aralkoxyalkyl; a group --N═C(R₁₅) (R₁₆); a group--(CH₂)_(n") CH(R₁₇) (R₁₈);

a group ##STR13##

R₁₅ and R₁₆ are independently hydrogen or alkyl,

R₁₇ and R₁₈ are independently S(O)_(n) alkyl, COOR₉, alkoxy, amino,substituted amino, benzyloxy, trimethylsilyl, cyano, --C(R₁₉)SR₂₀ oradditionally one thereof may be hydrogen.

R₁₉ is hydrogen or alkyl,

R₂₀ is alkyl or aryl,

R₉, R₁₀ and R₁₁ are independently hydrogen, alkyl, haloalkyl,alkoxyalkyl, unsubstituted or substituted aryl or unsubstituted orsubstituted aralkyl,

n and n" are independently zero, one or two, and

X₄ is oxygen or sulfur.

When R is a carbamoyl group or a mono- or di-substituted carbamoyl groupit is preferably of formula CONR₇ R₈ wherein R₇ and R₈ are independentlyhydrogen or an aliphatic or a saturated or unsaturated cyclic orheterocyclic group each of which may be unsubstituted or substituted.

R₇ and R₈ are preferably each independently a) hydrogen; halogen; b)alkyl, alkenyl, alkynyl, alkoxy, alkoxyalkoxy, alkenyloxy, alkynyloxy,alkylS(O)_(p), alkenylS(O)_(p) or alkynylS(O)_(p), alkylS(O)_(p) alkyl,alkenylS(O)_(p) alkyl, alkylnylS(O)_(p) alkyl, each of which may in turnbe substituted by 1 to 6 halogen atoms or hydroxy and each of which maybe attached to the adjacent nitrogen atom via alkyl; c) acyl, acylalkyl,acyloxy or acyloxyalkyl; d) cycloalkyl, cycloalkylalkyl, heterocyclyl,heterocycloalkyl, heterocycloalkoxy, aryl, aralkyl, aryloxy, aralkoxy,arylS(O)_(p), aralkylS(O)_(p) or arylS(O)_(p) alkyl, each of which isunsubstituted or may be substituted by 1 to 3 substituents selected from(i) halogen; (ii) alkyl, alkenyl, alkynyl, alkoxy, alkoxyalkoxy,alkenyloxy, alkynyloxy, alkylS(O)_(p), alkenylS(O)_(p) oralkynylS(O)_(p), alkylS(O)_(p) alkyl, alkenylS(O)_(p) alkyl,alkynylS(O)_(p) alkyl, each of which may in turn be substituted by 1 to6 halogen atoms; and (iii) nitro, cyano, acyl, amino or substitutedamino, aminosulfonyl; aminoalkyl or substituted aminoalkyl; e ) amino,substituted amino, amido, substituted amido; aminosulfonyl, cyano,nitro; or ##STR14## wherein Y₄ ' is hydrogen, lower alkyl, lower alkoxyor hydroxy and n"' is 0, 1, 2 or 3, and

p is 0, 1 or 2.

R₄ ' is as defined for Y₁.

X or Y as carbamoyl is also preferably of formula CONR₇ R₈ as definedabove.

When R is carboxyl in salt form the salt is preferably formed with analkali metal, alkali earth metal, optionally substituted ammoniumcation, a trialkyl sulfonium cation, a trialkylsulfoxonium cation or aphosphonium cation, especially the cation of an alkali metal (e.g. theLi or Na cation) or of an earth alkali metal (e.g. the Ca or Mg cation);the ammonium cation; a substituted ammonium cation [such as a C₁₋₅alkylammonium cation, a di--C1-5-alkylammonium cation, a tri-C₁₋₅alkylammonium cation, a tetra-C₁₋₅ ammonium cation, a (C₁₋₅alkoxy-alkyl)ammonium cation, a (hydroxy--C₁₋₅ alkyl)ammonium cation]; aphosphonium cation; a tri(C₁₋₈ alkyl)sulfonium cation; or a tri(C₁₋₈alkyl)sulfoxonium cation.

When Y₁, Y₂ and/or Y₃ is a carboxyl group this may be in ester or saltform or in amide form (i.e. a carbamoyl) and as such is as describedabove for R in these forms. Where A has meaning g) it contains one tothree heteroatoms and signifies for example thienyl, furanyl, pyrrolyl,oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, imidazolyl, pyrazolyl,oxadiazolyl or thiadiazolyl.

Where A has one of the above defined heteroaromatic significances, b)through g), the substituted hetero ring is particularly selected frompyridyl, quinolyl, pyridyl-N-oxide, pyrimidinyl, pyrazinyl, thienyl orfuryl, more particularly from pyridyl or thienyl.

Alkyl moieties unless otherwise specified contain 1 to 8 carbon atoms,preferably 1 to 5, especially 1 to 4, e.g. 1 or 2 carbon atoms. Loweralkyl moieties contain 1 to 4, e.g. 1 or 2 carbon atoms. Alkyl moietiesas are present in R₅, R₇ or R₈ contain 1 to 24 preferably 1 to 12,especially 1 to 6 carbon atoms whereby one of R₇ and R₈ is preferablyhydrogen when the other is alkyl.

Alkyl moieties as bridging groups may be straight chain or branched andpreferably contain 1 to 4, e.g. 1 or 2 carbon atoms. They may beoptionally substituted by aryl or substituted aryl and may optionally beinterrupted by or attached via an oxygen or sulfur atom.

"Conjugated alkoxy" stands for an alkoxy group interrupted in its alkylmoiety by one or more oxygen atoms eg alkoxyalkoxy, alkoxyalkoxyalkoxy,etc.

Alkenyl and alkynyl moieties contain 2 to 8, preferably 2 to 4,especially 2 or 3 carbon atoms.

Halogen is preferably F, Cl or Br, especially Cl.

Aryl moieties are preferably as defined for meanings a) to g) of ringsystem A or as ring B and preferred meanings of each, especially phenyl.Such aryl moieties may be unsubstituted or substituted and in the lattercase carry 1 to 3 substituents as defined for Y₁ unless otherwisespecified.

Substituted amino, -amido, -aminoxy, -aminoalkyl, -iminoxy, -carbamoyl(other than as R) is preferably substituted by one or two substituentsselected from alkylalkoxy, haloalkyl, acyl, alkoxyalkyl, unsubstitutedor substituted aryl or unsubstituted or substituted aralkyl.

Substituted methylene is preferably substituted by one or two groups asdefined for Y₁.

Acyl as or as part of a substituent is conveniently ##STR15## whereinR"' is as defined for Y₁ [for example alkyl, haloalkyl, cycloalkyl,alkoxyalkyl, unsubstituted or substituted aryl (especially phenyl)].Examples of acyl include acetyl, propionyl, butyryl, unsubstituted orsubstituted benzoyl, pivaloyl or chloracetyl, especially acetyl orunsubstituted or substituted benzoyl.

Cycloalkyl is preferably of 3 to 6 carbon atoms especially cyclopropyl,cyclopentyl or cyclohexyl, heterocyclo is preferably 5 or 6 membered andas defined for A definitions b) to g) and preferences or saturated andcontaining O, S or N as heteroatom, eg tetrahydrofuryl, piperidinyl,morpholinyl.

For convenience bridging members such as ##STR16## are so written butare to be understood as embracing ##STR17##

Carbamoyl or substituted carbamoyl moieties are attached to the moleculewhich they substitute via their carbonyl. Amido or substituted amidomoieties are attached to the molecule which they substitute via theirnitrogen atom.

A particular group of compounds of formula I (compounds Ia) comprisesthose wherein ring system A is selected from phenyl, pyridyl orpyridyl-N-oxide.

R is a carboxyl group which may be in the form of the free acid or inester or salt form, a thiocarboxyl group which may be in the form of thefree acid or in ester form, a carbamoyl group or a mono- or di-substituted carbamoyl group.

Y₁, Y₂ and Y₃ are attached to carbon atoms and are independentlyhydrogen, halogen, alkyl, alkoxy;

each of W₁, W₂, W₃, W₄ and W₅ is independently CH, CR₃ or nitrogen;

W₆ is NH or oxygen;

Z is a 2- or 3-membered bridge comprised of elements selected frommethylene, substituted methylene or ##STR18##

R₁ and R₃ each is independently hydrogen, halogen, alkyl, alkoxy,aryloxy or aralkoxy.

X and Y each is independently hydrogen, hydroxy, cyano, alkoxy, acyloxyor together represent ═O; or

X and R together form a bridge having the formula ##STR19## wherein thecarbonyl is attached to A.

When R is carboxyl or thiocarboxyl in ester form it is preferably offormula --COOR₅ or COSR₅ ;

wherein each R₅ is independently alkyl, alkoxyalkyl, alkenyl, alkynyl,substituted aryl or unsubstituted or substituted aralkyl.

When R is carboxy or thiocarboxyl in salt form the salt is preferablyformed with an alkali metal, alkali earth metal, optionally substitutedammonium cation especially the cation of an alkali metal (e.g. the Li orNa cation) or of an earth alkali metal (e.g. the Ca or Mg cation); theammonium cation; a substituted ammonium cation [such as a C₁₋₅alkylammonium cation, a di-C₁₋₅ alkylammonium cation, a tri-C₁₋₅alkylammonium cation, a tetra-C₁₋₅ ammonium cation.

When R is carbamoyl or mono- or di- substituted carbamoyl it ispreferably of formula CONR₇ R₈ wherein R₇ is hydrogen, alkyl, haloalkyl,alkoxyalkyl, unsubstituted or substituted aryl or unsubstituted orsubstituted aralkyl and R₈ is hydrogen, alkyl, NH₂, NHR₆ or OR₆ whereinR₆ is as defined for R₇.

A particular compound group (compounds Ib) comprises those compounds offormula I wherein ring system A represents phenyl, pyridyl or thienyl; Brepresents pyrimidinyl or triazinyl; R represents a ring C especiallyoxazole, oxazolone, oxazolidine or oxazolidinone; carboxyl in the formof the free acid or in ester or salt form; substituted carbamoyl, cyanoor together with X represent ##STR20## Y₁, Y₂ and Y₃ each representindependently hydrogen, halogen, alkyl, alkoxy, alkylthio or arylthio.

X, Y each represent independently hydrogen, hydroxy, alkoxy, acyloxy, aring B, halogen, alkylthio or arylthio or together ═O or ═NH

and R₁ and R₃ each represent independently halogen, alkoxy, alkyl,haloalkoxy, optionally substituted aryloxy, aralkoxy, alkylnyloxy,alkenyloxy.

A further compound group comprises compounds Ib wherein Y₁, Y₂ and Y₃additionally may each represent independently aralkoxy, alkenyloxy oralkynyloxy.

B is especially pyrimidinyl, particularly 4,6-dimethoxy-2-pyrimidinyl.

A is especially phenyl or pyridyl substituted as defined above.

X and Y are preferably hydrogen, halogen, cyano, hydroxy, alkoxy ortogether ═O, especially hydrogen, hydroxy or together ═O.

A further group of compounds according to the invention (Compounds Ic)comprises those of formula I wherein ring system A is pyridyl,

R is CONR₇ 'R₈ '

wherein R₇ ' and R₈ ' represent independently hydrogen, alkoxy, alkyl;or aryl or aralkyl each of which may be unsubstituted or substituted,

X is hydrogen,

Y is OR₃ ', SR₃ ' or OCOR₃ '

wherein R₃ ' is alkyl; or aryl; or aralkyl each of which may beunsubstituted or substituted,

or X and Y together represent ═O or ═S and ring system B is m--CF₃phenyl.

Within the group Ib, compounds are preferred wherein X is OH and Y is Hor X and Y together represent ═O, A is 2- or 3-pyridyl, R₇ is hydrogenor alkyl especially methyl, R₈ is phenyl or benzoyl which may beunsubstituted or substituted eg 1-3 times by halogen, alkyl and/oralkoxy. The following meanings are preferred independently for eachsubstituent.

A a) meanings a) and b)

b) phenyl

c) pyridyl

R a) carboxyl in the form of the free acid or in salt or ester form orcarbamoyl or mono- or di-substituted carbamoyl

b) COOR₅ wherein R₅ is hydrogen, alkyl, COO⁺ Ma⁻ wherein Ma is an alkalimetal or ammonium cation or CONR₇ R₈ wherein R₇ is hydrogen or alkyl andR₈ is alkyl, aryl or substituted aryl

c) COO⁻ Na⁺, COOCH₃, CONHC₆ H₁₃, CONH(CH₃)phenyl, COO⁻ H₃ N⁺ iC₃ H₇,CON(CH₃)₂, CONHCH₃

Y₁ a) hydrogen, halogen, alkyl or alkoxy

b) halogen, especially fluorine or chlorine

Y₂, Y₃ a) hydrogen or halogen, alkyl or alkoxy

b) hydrogen or halogen

c) chlorine

W₁ N

W₂ a) CH or N

b) CH

W₃ CR₃

W₄ N

W₅ a) CH or N

b) N

W₆ a) O

b) NH

Z a) elements selected from methylene, substituted methylene, ##STR21##X₁, X₂ a) alkoxy, especially methoxy b) hydroxy

X₃ a) hydrogen

b) alkoxy especially methoxy

R₁, R₃ a) alkoxy, especially methoxy

R₄ a) halogen, especially chlorine

b) alkyl, especially methyl

R₂ a) alkyl, especially methyl

b) hydrogen

R₅ a) alkyl, alkenyl or alkynyl

b) C₁₋₄ alkyl, especially methyl or ethyl

c) C₂₋₄ alkenyl

d) C₂₋₄ alkynyl, especially propargyl

R₆, R₇ a) alkyl

b) methyl, ethyl

R₈ a) hydrogen

b) alkyl, especially methyl or ethyl

c) an aryl, especially a phenyl

R₉, R₁₀, a) hydrogen or alkyl

R₁₂, R₁₅, R₁₉ b) hydrogen or methyl

R₁₁ a) alkyl

b) propyl (n- or iso-)

Y₄ a) alkyl or alkoxy

b) CH₃ or CH₃ O

R₁₃, R₁₄ a) hydrogen or halogen

b) hydrogen or fluorine

R₁₆ a) alkyl

b) C₁₋₄ alkyl, especially methyl or ethyl

R₁₇ a) S(O)_(n) alkyl or COOR₉

b) SO₂ CH₃ or COOCH₃

R₁₈ a) hydrogen

R₂₀ a) alkyl or phenyl

b) methyl or phenyl

n a) 2 b) 0

n' a) 2 b) 3

n" a) 1 b) 0

m a) 1 b) 2

X a) hydroxy

b) hydrogen

c ) taken with Y, ═O

d) acyloxy

e) alkoxycarbonyloxy

f) carbamoyloxy

g) sulphonyloxy

Y a) taken with X, ═O

b) hydrogen

X+R ##STR22## R' a) alkyl b) alkoxy R" a) alkyl

b) methyl

R"' a) alkyl

b) aryl, especially phenyl

Ring A, Ring B a) at least one contains a heteroatom

b) ring A=a phenyl or a pyridine ring B=a pyrimidine especially 3,5dimethoxy pyrimidine

Combinations Of the above listed preferred meanings are especiallypreferred. One such combination comprises compounds of formula (I) inwhich

A is phenyl or pyridyl;

R is a carboxyl group in the form of a free acid, ester or salt;carbamoyl; especially COOR₅ " wherein R₅ " is C₁₋₅ alkyl or C₂₋₅ alkenylor CONR₇ "R₈ " wherein

R₇ " is C₁₋₁₂ alkyl, amino, C₁₋₄ alkylamino, anilino, haloanilino,benzyl, halobenzyl, C₁₋₄ alkylbenzyl, C₁₋₄ alkoxybenzyl, phenyl,halophenyl, C₁₋₄ alkylphenyl or C₁₋₄ alkoxyphenyl;

R₈ " is hydrogen or C₁₋₄ alkyl;

Y₁, Y₂ and Y₃ are independently hydrogen or halogen;

W₁ and W₄ are N;

W₂ is CH;

W₃ is CR₃ wherein R₃ is C₁₋₅ alkoxy;

R₁ is C₁₋₅ alkoxy;

X is hydroxyl or C₁₋₄ alkoxycarbonyloxy or taken with Y is ═O;

Y is hydrogen or taken with X is ═O; or

X and R together form a bridge having the formula --C(O)O-- wherein thecarbonyl is attached to A, and Y is hydrogen or C₂₋₈ acyloxy.

A further group of compounds includes those of formula I wherein X mayadditionally represent COOR₅ as defined above; and/or R₁₅ and R₁₆ mayadditionally independently represent halogen, alkylthio, alkoxycarbonylor optionally substituted carbamoyl; and/or R₁₈ may additionallyrepresent optionally substituted aryl.

Further preferred substituent meanings include compounds according toclaim 1 wherein A is other than phenyl, naphthyl, pyridyl which may befused on its (b) or (c) side to benzene, or pyridyl-N-oxide.

Compounds according to claim 1 wherein R is other than formyl, acarboxyl group which may be in the form of the free acid or in ester orsalt form, a thiocarboxyl group which may be in the form the free acidor in ester form or the group CX₁ X₂ X₃.

Compounds according to claim 1 wherein R is other than formyl,dimethoxymethyl, COOR₃₀ or COSR₃₁ wherein R₃₀ represents hydrogen, analkali metal cation, an alkaline earth metal cation, an ammonium cation,an alkylammonium cation, C₁₋₃ alkyl, C₂₋₃ haloalkyl, allyl, propargyl,benzyl optionally substituted by halogen, methyl, ethyl, methoxy,ethoxy, trifluoromethyl, methylthio, methylsulfinyl, methylsulfonyl ornitro, C₂₋₄ alkoxyalkyl, N═CR₃₂ R₃₃, CH₂ S(O)_(t) R₃₄ or CH(CH₃)S(O)_(t)R₃₄ wherein R₃₂ is chlorine, methyl, ethyl or methylthio, R₃₃ is methyl,ethyl, COOCH₃, COOC₂ H₅ or C(O)N(CH₃)₂, R₃₄ is methyl, ethyl, propyl,isopropyl or phenyl optionally substituted by halogen, methyl, methoxyor nitro and t is 0, 1 or 2; and R₃₁ represents methyl, ethyl or benzyl.

Compounds of formula I wherein A is pyridyl or pyridyl-N-oxide and atleast two of Y₁, Y₂ and Y₃ are other than hydrogen.

Compounds of formula I wherein one of Y₁, Y₂ and Y₃ is other thanhydrogen, fluorine, chlorine, methyl, methoxy, methylthio,methylsulfinyl or methylsulfonyl.

Compounds of formula I wherein A is phenyl and one of Y₁, Y₂ and Y₃ isother than hydrogen, fluorine, chlorine, methyl, ethyl, methoxy, ethoxy,C₂₋₃ -alkenyl, C₂₋₃ alkynyl, SO.sub.(t) CH₃, SO.sub.(t) C₂ H₅, nitro,phenoxy, C₂₋₄ alkylcarbonyl, C(OCH₃)₂ CH₃ or C(SCH₃)₂ CH₃ and t is 0, 1or 2.

Compounds of formula I wherein each of Y₁, Y₂ and Y₃ is other thanhydrogen.

Compounds of formula I wherein one of W₁ and W₄ is other than nitrogen.

Compounds of formula I wherein W₂ is other than nitrogen or CH.

Compound of formula I wherein R₁ is other than methoxy or ethoxy.

Compound of formula I wherein W₃ is other than CR₃ wherein R₃ is methyl,ethyl, methoxy, ethoxy, difluormethoxy, or chlorine.

Compounds of formula I wherein both of X and Y are other than hydrogen.

Compounds of formula I wherein one of X and Y is other than hydrogen,fluorine, chlorine, methyl, hydroxy, cyano, carbamoyl, methylcarbamoyl,dimethylcarbamoyl or COOR₃₅, wherein R₃₅ is C₁₋₃ alkyl, C₂₋₅ haloalkyl,C₃₋₅ alkenyl, C₃₋₅ alkynyl, C₂₋₅ alkoxyalkyl, or benzyl optionallysubstituted by methyl, methoxy, methylthio, trifluoromethyl, halogen ornitro.

Combinations of these further preferred meanings with each other andwith those set out above also deserve mention.

Examples of preferred compounds according to the invention are compoundnos. 13, 40, 53, 55, 58, 64, 77, 78, 82, 91, 103, 108, 110, 111, 124,125, 130, 143, 149, 163, 170, 175, 183, 199, 204, 205, 211, 219, 220,224, 228, 247, 249, 258, 262, 263, 265, 266, 267, 272, 273, 277, 286,294, 302, 310, 385, 403, 413, 452, 454, 455, 456, 457, 464, 473, 477,479, 480, 481, 483, 487, 489, 504, 510, 522, 528, 531, 532, 539, 545,547, 571, 576, 584, 590, 591, 593, 594, 595,599, 605, 606, 607, 608,612and 622.

Compounds having the formula ##STR23## especially those wherein X is CNand at least one of W₁ and W₄ is nitrogen may exist in the alternatetautomeric form ##STR24##

The compounds of formula I according to the invention may be prepared asfollows.

a) when X and R combine to form a bridging group as defined above and Yis hydrogen, cyano, arylthio, arylsulfinyl or arylsulfonyl, reacting acompound of formula II ##STR25## wherein A is as defined above, Y'represents hydrogen, cyano, arylthio, arylsulfinyl or arylfulfonyl andZ₁ represents oxygen, sulfur or NR₂ wherein R₂ is as defined aboveexcept for hydrogen, with a compound of formula III ##STR26## whereinW₁, W₂, W₃, W₄ are as defined above except that at least one of W₁ andW₄ is nitrogen and R₂₁ represents methylsulfonyl, or halogen to obtainthe corresponding compound of formula Ip ##STR27## b) treating acompound of formula Ip wherein Y' represents cyano or arylsulfonyl andZ' represents oxygen and the other symbols are as defined above.

(i) by hydrolysis to give a corresponding compound of formula I whereinR and X form a bridge and Y is hydroxy or a compound of formula Iwherein X and Y together form ═O

(ii) with an amine to give a corresponding compound of formula I whereinR is an optionally substituted carbamoyl group and X and Y together form═O

(iii) with a group

    MOR.sub.22

wherein M an alkali metal and R₂₂ is alkyl, to give a correspondingcompound wherein R and X form a bridge and Y is alkoxy

c) hydrolyzing a compound of formula Ip wherein Y' represents hydrogenand Z₁ represents oxygen to give a compound of formula I wherein R is acarboxyl group optionally in salt form, X is hydrogen and Y is hydroxy

d) ring opening a compound of formula Ip wherein Y' represents hydroxyand Z₁ represents oxygen to give a compound of formula I wherein R is acarboxyl group optionally in salt form and X and Y together are ═O

e) esterifying a compound of formula I wherein R is a carboxyl groupoptionally in salt form and X and Y are ═O to give the correspondingcompound wherein R is a carboxyl group in ester form

f) halogenating a compound of formula Ip wherein Y' represents hydroxyto give a compound of formula I wherein X and R together form a bridginggroup and Y' is halogen

g) reacting a compound of formula Ip wherein Z₁ is oxygen and halogenrich a group R₂ NH₂ and a group HOR₂₃ wherein R₂₃ represents alkyl, acylor aryl and R₂ is as defined above to give the corresponding compoundwherein Z₁ is NR₂ and Y' is alkoxy, aryloxy or acyloxy

h) oxidizing a compound of formula Ip wherein Y' represents hydrogengive the corresponding compound wherein Y' represents hydroxy

i) reacting a compound of formula IV ##STR28## with a compound offormula V ##STR29## to produce a compound of formula Iq ##STR30##wherein A, R, R₁, W₁, W₂, W₃, W₄, Y₁, Y₂ and Y₃ are as defined above andX" and Y" are hydrogen and R₂₄ is alkyl, especially methyl, cyanomethyl,alkoxycarbonylmethyl, carbamoylmethyl,

j) mono- or di- halogenating a compound of formula Iq wherein X" and Y"are hydrogen to produce the corresponding compound of formula Iq whereinone or both of X" and Y" are halogen

k) oxidizing a compound of formula Iq wherein X" and Y" are bothhydrogen or X" is halogen and Y" is hydrogen to produce thecorresponding compound wherein X" and Y" together represent ═O or onerepresents hydrogen and the other represents hydroxy

l) alkylating a compound of formula Iq wherein X" represents hydrogenand Y" represents hydrogen to produce the corresponding compound whereinX" represents alkyl and Y" represents hydrogen

m) introducing an alkoxy or alkylthio group into a compound of formulaIq wherein X" represents halogen and Y" represents hydrogen to producethe corresponding compound wherein X" represents alkoxy or alkylthio andY" represents hydrogen

n) acylating a compound of formula Iq wherein X" represents hydroxy andY represents hydrogen to produce the corresponding compound wherein X"represents acyloxy and Y" represents hydrogen

o) reacting a compound of formula Ip wherein Z₁ is oxygen and Y' ishydrogen with a group R₇ NH₂ wherein R₇ is as defined above to give acompound of formula I wherein R is monosubstituted carbamoyl, X ishydrogen and Y is hydroxy

p) sulfonylating, carbamoylating, acylating or carbalkoxylating acompound of formula Ip wherein Z₁ is oxygen and Y' is hydroxy to producethe corresponding compound of formula Ip wherein Y' representssulfonyloxy, carbamoyloxy, acyloxy or alkoxycarbonyloxy

q) reacting a compound of formula Ip wherein Z₁ is oxygen and Y' ishalogen with a group R₇ R₈ NH wherein R₇ and R₈ are as defined above (R₇and R₈ ≠H) to give a compound of formula I wherein R is disubstitutedcarbamoyl, and X and Y together represent ═O.

r) oxidizing a compound of formula ##STR31## to give a correspondingcompound of formula I wherein X and Y together represent ═O.

s) reacting a compound of formula III with a compound of formula IV eachas defined above to produce a compound of formula Iq wherein X" and Y"are hydrogen.

t) oxidizing a compound of formula I wherein X═Y═H to give a compound Ipwherein Z₁ is oxygen and Y' is hydroxy.

u) reacting a compound of formula V ##STR32## with a compound of formulaIV wherein R is cyano and R₂₄ is halogen and oxidizing the product togive a compound of formula I where R is cyano and X and Y togetherrepresent ═O or of formula Ip wherein Z₁ represents ═O and Y¹ is cyano.

and in each case recovering any compound wherein R is a carboxyl orthiocarboxyl group in free form or in ester form and any compoundwherein R is carboxyl in free form or in salt form.

The following table is illustrative of suitable reaction conditions.

    __________________________________________________________________________    REACTION CONDITIONS                                                           Reaction Reagents Solvents        Temperature                                                                             Others                            __________________________________________________________________________    a)                                                                              1) a) base eg LDA                                                                             1) and 2) inert eg DMF,                                                                       a) reduced eg -70°                     or b) base eg NaH                                                                             ether, cyclic ether eg THF                                                                    b) R.T.                                       2) III          1) and 2) inert eg DMF,                                                       ether, cyclic ether eg THF                                  b)                                                                              i)1) base eg NaOH                                                                             inert eg ether, R.T.                                          2) acidify      cyclic ether eg THF or                                                        alcohol eg methanol                                         b)                                                                              ii) 1) amine    inert eg ether, cyclic                                                        ether eg THF                                                b)                                                                              iii) MOR.sub.22 alcohol eg methanol,                                                          cyclic ether eg THF                                         c)                                                                              base eg LiOH    water optionally with an alcohol                                                              R.T.                                                          or cyclic ether eg THF                                      d)                                                                              base eg NaOH    as c)           R.T.                                        e)                                                                              halide eg IR.sub.5                                                                            inert eg DMF,   elevated eg                                   base eg K.sub.2 CO.sub.3, NaH                                                                 2-butanone (MEK)                                                                              50-80°                               f)                                                                              halogenating    inert eg chlorinated                                                                          elevated eg                                   agent eg SOCl.sub.2, DMF                                                                      hydrocarbon eg CCl.sub.4 CH.sub.2 Cl.sub.2                                                    40-80°                               g)                                                                              1)R.sub.7 NH.sub.22 ; R.sub.23 OH                                                             as f)           elevated eg                                                                   50-80°                               h)                                                                              1) oxidizing agent                                                                            1), 2) and 3) inert eg                                                                        elevated eg 50°                        eg NaOCl        H.sub.2 O optionally with alcohol                                                             R.T.                                          2) base eg NaOH eg methanol                                                   3) acid eg HCl  cyclic ether eg THF                                                                           R.T.                                        i)                                                                              1) base eg LDA  1) anhyd. inert eg ether such                                                                 reduced eg -30°                                        as cyclic ether eg THF                                        2) AcOH         2), 3) and 4) ether, H.sub.2 O                                                                R.T.                                          3) DDQ                          reduced eg 0°                          4) aq NaOH                      elevated eg 75°                      j)                                                                              NBS, benzoylperoxide                                                                          inert eg halogenated                                                                          elevated eg 75°                                        hydrocarbon such as CCl.sub.4                               k)                                                                              A. when X" = halogen and                                                                      DMSO            elevated eg 50-60°                     Y" = H to give X + Y are = O                                                  DMSO, Na.sub.2 CO.sub.3                                                       B. when X" and Y" = H                                                                         AcOH            110°, 1 hr; or                         to give X" + Y" are = O                                                       a) SeO.sub.2                                                                  b) t-butylhydro-                                                                              CH.sub.3 CN     85°; or                                peroxide                                                                      Co.sub.2 (CO).sub.8                                                           c) 1) Mn (OAc).sub.3                                                                          AcOH            25→100°                         2) H.sub.2 O                                                                  C. when X" and Y" = H                                                         to give X" = OH, Y" = H                                                       i) nBuLi        THF             -78°                                   ii) t-butyl peroxybenzoate                                                                    THF             -78°→20°                 iii) BF.sub.3.MeOH                                                                            toluene         40°→100°               l)                                                                              base eg NaH, alkyl                                                                            inert eg ether, THF                                                                           0°→R.T.                         halide                                                                      m)                                                                              MOR.sub.22, MSR.sub.22                                                                        inert eg DMF, alcohol                                                                         R.T.→50°                        eg NaOCH.sub.3                                                                O                                                                           n)                                                                              acyl chloride eg CH.sub.3 CCl                                                                 inert eg ether, THF                                                                           R.T.→30°                        or anhydride eg Ac.sub.2 O;                                                                   pyridine                                                      amine eg triethylamine                                                      o)                                                                              amine, eg α-methyl                                                                      alcohol eg methanol                                                                           R.T.→80°                        benzylamine                                                                   or                                                                            amine, eg aniline,                                                                            inert eg toluene                                                                              R.T.                                          CH.sub.3 SO.sub.2 NH.sub.2 ; Me.sub.3 Al (catalyst)                                           CH.sub.2 Cl.sub.2                                           p)                                                                              acylchloride eg acetyl-                                                                       inert eg ether  R.T.                                          chloride, ethylchloro-                                                                        THF, pyridine                                                 formate or anhydride; amine                                                   eg DMAP, triethylamine                                                        or                                                                            isocyanate eg methylisocyanate;                                                               inert eg ether  "                                             amine eg triethylamine                                                                        THF, pyridine                                                 or                                                                            sulfonyl chloride eg methyl-                                                                  inert eg ether  "                                             sulfonyl chloride; amine eg                                                                   THF, pyridine                                                 triethylamine                                                               q)                                                                              R.sub.7 R.sub.8 NH, triethylamine,                                                            inert eg CH.sub.2 Cl.sub.2                                                                    "                                             DMAP                                                                        r)                                                                              i) m-chloroperbenzoic acid                                                                    inert eg CH.sub.2 Cl.sub.2                                                                    20°, 30 min                            ii) base eg NaOH                                                                              inert eg cyclic ether                                                                         20°, 30 min                          s 1) LDA          THF             -78°                                   2) III          THF             -78°→20°               t)                                                                              KMnO.sub.4      H.sub.2 O       100° C.                              u)                                                                              i) base eg K.sub.2 CO.sub.3, KOBu.sup.t,                                                      inert eg DMF, THF                                                                             RT→100° C.                      NaH                                                                           ii) oxidizing agent eg NaOCl                                                                  water optionally with inert                                                                   RT                                            or H.sub.2 O.sub.2 /AcOH                                                                      eg cyclic ether or CH.sub.3 CN                              __________________________________________________________________________

Processes a) through u) also form part of the invention.

The starting materials of formula II or III are either known or may beprepared analogously to known methods.

The compounds of formula I have herbicidal activity as observed aftertheir pre-emergent or post-emergent application to weeds or a weedlocus.

The term "herbicide" (or "herbicidal") refers to an active ingredient(or an effect) which modifies the growth of plants because of plantgrowth regulating or phytotoxic properties so as to retard the growth ofthe plant or damage the plant sufficiently to kill it.

Application of a compound of formula I is made according to conventionalprocedure to the weeds or their locus using a herbicidally effectiveamount of the compound, usually from 10 g to 10 kg/ha.

Compounds according to the invention may be used in the control of bothbroad-leaf and grassy weeds on both pre- and post-emergent application.Compounds may also exhibit selectivity in various crops and are thussuited for use in weed control in crops such as corn, cotton, wheat,soybean and rice.

The optimum usage of a compound of formula I is readily determined byone of ordinary skill in the art using routine testing such asgreenhouse testing and small plot testing. It will depend on thecompound employed, the desired effect (a phytotoxic effect requiring ahigher rate than a plant growth regulating effect), the conditions oftreatment and the like. In general satisfactory phytotoxic effects areobtained when the compound of formula I is applied at a rate in therange of from 0.01 to 5.0 kg, more preferably of from 0.05 to 2.5 kg perhectare, eg 0.05 to 5.0 kg per hectare, especially 0.1 to 2.5 kg perhectare.

The compounds of formula I may be advantageously combined with otherherbicides for broadspectrum weed control. Examples of herbicides whichcan be combined with a compound of the present invention include thoseselected from the carbamates, thiocarbamates, chloroacetamides,dinitroanilines, benzoic acids, glycerol ethers, pyridazinones,semicarbazones, uracils and ureas for controlling a broad spectrum ofweeds.

The compounds of formula I are conveniently employed as herbicidalcompositions in association with agriculturally acceptable diluents.Such compositions also form part of the present invention. They maycontain, aside from a compound of formula I as active agent, otheractive agents, such as herbicides or compounds having antidotal,fungicidal, insecticidal or insect attractant activity. They may beemployed in either solid or liquid forms eg in the form of a wettablepowder or an emulsifiable concentrate incorporating conventionaldiluents. Such compositions may be produced in conventional manner, egby mixing the active ingredient with a diluent and optionally otherformulating ingredients such as surfactants.

Agriculturally acceptable additives may be employed in herbicidalcompositions to improve the performance of the active ingredient and toreduce foaming, caking and corrosion, for example.

The term "diluent" as used herein means any liquid or solidagriculturally acceptable material which may be added to the activeconstituent to bring it in an easier or improved applicable form,respectively, to a usable or desirable strength of activity. It can forexample be talc, kaolin, diatomaceous earth, xylene or water.

"Surfactant" as used herein means an agriculturally acceptable materialwhich imparts emulsifiability, spreading, wetting, dispersibility orother surface-modifying properties. Examples of surfactants are sodiumlignin sulfonate and lauryl sulfate.

Particularly formulations to be applied in spraying forms such as waterdispersible concentrates or wettable powders may contain surfactantssuch as wetting and dispersing agents, for example the condensationproduct of formaldehyde with naphthylene sulphonate, an ethoxylatedalkylphenol and an ethoxylated fatty alcohol.

In general, the formulations include from 0.01 to 90% by weight ofactive agent and from 0 to 20% by weight of agriculturally acceptablesurfactant, the active agent consisting either of at least one compoundof formula I or mixtures thereof with other active agents. Concentrateforms of compositions generally contain between about 2 and 90%,preferably between about 5 and 70% by weight of active agent.Application forms of formulation may for example contain from 0.01 to20% by weight of active agent.

Typical herbicidal compositions, according to this invention, areillustrated by the following Examples A, B and C in which the quantitiesare in parts by weight.

EXAMPLE A Preparation of a Dust

10 Parts of a compound according to this invention and 90 parts ofpowdered talc are mixed in a mechanical grinder-blender and are grounduntil a homogeneous, free-flowing dust of the desired particle size isobtained. This dust is suitable for direct application to the site ofthe weed infestation.

EXAMPLE B Preparation of a Wettable Powder

25 Parts of a compound according to this invention are mixed and milledwith 25 parts of synthetic fine silica, 2 parts of sodium laurylsulphate, 3 parts of sodium ligninsulphonate and 45 parts of finelydivided kaolin until the mean particle size is about 5 micron. Theresulting wettable powder is diluted with water before use to a sprayliquor with the desired concentration.

EXAMPLE C Preparation of Emulsifiable Concentrate (EC)

13.37 Parts of a compound according to this invention are mixed in abeaker with 1.43 parts of Toximul 360A (a mixture of anionic andnon-ionic surfactants containing largely anionic surfactants), 5.61parts of Toximul 360A (a mixture of anionic and non-ionic surfactantscontaining largely nonionic surfactants), 23.79 parts ofdimethylformamide and 55.8 parts of Tenneco 500-100 (predominantly amixture of alkylated aromatics such as xylene and ethylbenzene) untilsolution is effected. The resulting EC is diluted with water for use.

The following examples are provided to illustrate the practice of thepresent invention. Temperature is given in degrees Celsius.Abbreviations used in this specification.

THF=tetrahydrofuran

LDA=lithium diisopropylamide

RT=room temperature

DMF=dimethylformamide

DDQ=2,3-dichloro-5,6-dicyanobenzoquinone

NBS=N-bromosuccinimide

DMSO=Dimethylsulfoxide

MEK=Methylethylketone

DMAP=4-Dimethylaminopyridine

Individual alkyl substituents listed in the following tables from A to Fare in the "n" isomeric form unless otherwise indicated.

EXAMPLE 1 7-chloro-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide (Table A,cpd. no. 6)

1.68 g (0.01 mol) of 7-chlorophthalide is added to 100 ml of dry THF andthe mixture cooled to -70° C. 6.8 ml (0.01 mol) of 1.5M LDA is thenadded over 3 minutes and the reaction mixture stirred at -70° C. for 15minutes. 2.18 g (0.01 mol) of 2-methylsulfonyl-4,6-dimethoxypyrimidinein 50 ml of THF is then added and the mixture stirred for 4 hrs withtemperature being maintained at -75° to -70° C. The reaction mixture isneutralized with 1.5 g of NH₄ Cl in 5 ml of water, warmed andconcentrated on a rotovaporator. The concentrate is partitioned betweenCH₂ Cl₂ /H₂ O (50 ml each) and the aqueous phase separated and treatedwith further 30 ml of CH₂ Cl₂. The combined CH₂ Cl₂ phases are washedwith 30 ml of water, separated and concentrated. The concentrate wasflash chromatographed on silica gel using 80/20 hexane/ethyl acetate(500 ml), 50/50 hexane/ethyl acetate (500 ml) and 80/20 acetone/methanol(500 ml) (30 fractions X 50 ml). The title compound (fractions 9-23) wasobtained after recrystalization from hexane/CH₂ Cl₂ as a white solid,m.p. 148°-149° C.

EXAMPLE 2 5-(4,6-dimethoxy-2-pyrimidinyl)-furo[3,4-b]pyridine-7(5H)-one(Table B, cpd. no. 40)

A solution of 1.3 g (0.0096 mols) of furo [3,4-b]pyridine-7(5H)-one in50 ml of dry THF is cooled to -75° C. and 8 ml (0.0192 mols) of 2.5M LDAadded dropwise over 5 minutes. The mixture is allowed to react for 1 hrat -75° C. and 2.1 g (0.0096 mol) of2-methylsulfonyl-4,6-dimethoxypyrimidine in 30 ml of dry THF addeddropwise over 10 minutes. The mixture is allowed to warm to RT, 1.6 mlof HCl added and the THF evaporated off. The residue is dissolved in 75ml of CH₂ Cl₂, washed with water (2×50 ml) and the organic phaseconcentrated to give a yellowish white gummy solid. This ischromatographed on a silica gel column using 50/50 hexane/ethyl acetate(500 ml), ethyl acetate (500 ml) and 80/20 acetone/methanol (1000 ml)(30 fractions). The crystalline residue (fractions 18-21) of the titleproduct has m.p. of 167°-168° C.

EXAMPLE 37-chloro-3-methoxy-3-(4,6-dimethoxy-2-pyrimidinyl)-2-methyl-isoindol-1(3H)-one(Table C, cpd. no. 54)

A mixture of 0.5 g of7-chloro-3-hydroxy-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide, 30 ml ofCCl₄, 2 ml of SOCl₂ and 4 drops of DMF is heated at 65° C. for 11/2 hrs,cooled and excess SOCl₂ and CCl₄ removed on a rotovaporator. The residueis diluted with 20 ml of CH₂ Cl₂ and added to a mixture of 5 ml of 40%aq methylamine and 10 ml of methanol with stirring over 1/2 hr. Themixture is placed on a rotovaporator and the residue partitioned between50 ml each of CH₂ Cl₂ and water. The organic phase is concentrated andflash chromatographed on silica gel using 50/50 hexane/ethyl acetate(800 ml), ethyl acetate (500 ml) and 80/20 acetone/methanol (200 ml) (30fractions X 50 ml). The product (fractions 19-21) was obtained as ayellow gum.

EXAMPLE 4 7-chloro-3-hydroxy-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide(Table A, cpd. no. 13)

A mixture of 1.8 g of7-chloro-3-cyano-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide, 50 ml of 1%NaOH and 50 ml of THF are stirred at room temperature for 3 hrs. The THFis removed by evaporation and the mixture is diluted with water andextracted twice with ethyl acetate. The aqueous solution is acidifiedwith 2N--H₂ SO₄. The resulting acid solution is extracted with 3×100 mlethyl acetate and the organic phases combined, dried over Na₂ SO₄ andconcentrated to give a pale yellow solid. This residue is taken up inethyl acetate and treated with activated charcoal until the yellow baseline material is removed to give the title product as a white solid m.p.188°-190° C.

EXAMPLE 5 7-chloro-3-methoxy-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide(Table A, cpd. no. 30)

1.0 g of 7-chloro-3-cyano-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide isslurried in 20 ml of methanol and the solution cooled with ice and 0.6ml of sodium methoxide added dropwise. After stirring for 10 min afurther 1 ml of sodium methoxide is added and stirring continued for 10min and the mixture is then quenched with 2N H₂ SO₄. Methanol is removedon a rotovaporator and the residue partitioned between water and ethylacetate. The organic phase is dried over Na₂ SO₄ and concentrated. Flashchromatography of the residue over silica gel using 25% ethylacetate/hexane yields a white solid m.p. 180°-183° C.

EXAMPLE 6 a) Methyl2-chloro-6-(4,6-dimethoxy-2-pyrimidinylcarbonyl)benzoate (Table C, cpd.no. 55), and b) 7-chloro-3-chloro-(4,6-dimethoxy-2-pyrimidinyl)phthalide(Table A, cpd. no. 21)

A mixture of 0.7 g of7-chloro-3-hydroxy-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide, 30 ml ofCCl₄, 2 ml of SOCl₂ and 4 drops of DMF are refluxed at 60° for 11/2 hrs.The mixture is then cooled, excess SOCl₂ and CCl₄ removed on arotovaporator. The residue is diluted with 20 ml of CH₂ Cl₂ and added toa stirred mixture of 10 ml of methanol and 2 ml of diethylamine. After21/2 hrs the mixture is stripped on a rotovaporator to remove excess CH₂Cl₂ and methanol and the residue partitioned between CH₂ Cl₂ (50 ml) andwater (50 ml). The organic phase is separated, concentrated and thegummy residue flash chromatographed over silica gel using 80/20hexane/ethyl acetate (500 ml), 60/40 hexane/ethyl acetate (500 ml) (28fractions X 50 ml). Fractions 18 to 20 yielded title compound a) andfractions 11 to 16 the compound b).

EXAMPLE 7 7-chloro-3-cyano-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide(Table A, cpd. no. 27)

600 mg of 7-chloro-3-cyanophthalide are added to an ice-cold suspensionof hexane washed 60% NaH (160 mg) in DMF (20 ml). After 15 min, 710 mgof 2-methylsulfonyl-4,6-dimethoxypyrimidine are added. After stirring atRT for 11/2 hr the mixture is poured onto 200 ml of ice/water acidifiedwith 2N H₂ SO₄ and stirred. The precipitate is filtered and dried in avacuum oven to yield the title product, m.p. 159°-161° C.

EXAMPLE 8 7-chloro-3,3-bis(4,6-dimethoxy-1,3,5-triazin-2-yl)phthalide(Table A, cpd. no. 36)

1.48 g of 7-chlorophthalide are dissolved in 80 ml of THF. The solutionis cooled to -70° C. and 1.5M LDA in THF (6 ml) is syringed in at -70°C. over 3 min. Stirring is continued for 15 min at -70°, 1.54 g of2-chloro-4,6-dimethoxy-1,3,5-triazine in 50 ml of THF added dropwise andthe mixture is then allowed to warm to -20°. The mixture is again cooledto -70° and 1 ml of conc. HCl in 10 ml of water is added. The mixture isstirred for 25 min and allowed to warm to RT and the THF is removed byevaporation. The residue is partitioned between CH₂ Cl₂ and water (50 mleach) and the aqueous phase extracted with an additional 30 ml of CH₂Cl₂. The combined organic phases are washed with 30 ml of water andconcentrated to give a yellow gum. This is flash chromatographed onsilica gel using 60/40 hexane/ethyl acetate (1000 ml), ethyl acetate(400 ml), 80/20 acetone/methanol (500 ml) (30 fractions X 50 ml, 1 X 200ml). Fractions 21 and 22 yielded a yellow gum which uponrecrystalization from hexane yielded title product m.p. 126°-127° as ayellow solid.

EXAMPLE 9 Lithium2-chloro-6-(4,6-dimethoxy-e-hydroxy-2-pyrimidinylmethyl)benzoate (TableC, cpd. no. 53)

A mixture of 1.0 g of 7-chloro-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide,0.136 g of LiOH.H₂ O, 2 ml of water and 10 ml of methanol is stirredovernight at RT. The mixture is evaporated to dryness on arotovaporator. Further drying in a drying pistol yield the titlecompound as a white solid, m.p. 153°-157° C.

EXAMPLE 10 Lithium3-[(4,6-dimethoxy-α-hydroxy-2-pyrimidinyl)methyl]pyridine-2-carboxylate(Table E, cpd. no. 64)

A mixture of 0.490 g of 5-(4,6-dimethoxy-2-pyrimidinyl)furo[3,4,b]-pyridine-7(5H)-one, 0.0768 gm of LiOH.H₂ O, 10 ml of methanoland 2 ml of water is stirred for 24 hrs under nitrogen at RT and thesolvent stripped off. The yellowish solid is dried for a further 2 hrsto yield the title product, m.p.>250° C. (decomp.).

EXAMPLE 11 Sodium2-chloro-6-[(4,6-dimethoxy-2-pyrimidinyl)carbonyl]benzoate (Table C,cpd. no. 58)

1.24 g of 7-chloro-3-hydroxy-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide,154 mg NaOH, 25 ml THF and 25 ml water are mixed until a yellowhomogenous solution is achieved. The solvents are stripped on arotovaporator and then on a Kugelrohr at 100° C. to produce the titlecompound as a yellow solid, m.p. 276°-278° C.

EXAMPLE 123-[(4,6-dimethoxy-2-pyrimidinyl)carbonyl]-pyridine-2-carboxylic acid(Table E, cpd. no. 63)

490 mg of 5-(4,6-dimethoxy-2-pyrimidinyl)-furo[3,4-b]pyridine-7(5H)-oneis dissolved in 50 ml of methanol and the mixture heated with stirringat 50° C. until a homogenous solution is formed (ca 1/2 hr). 2.6 g ofNaOCl is added dropwise and the solution heated for a further 1/2 hr at55° C. 0.208 g of 50% NaOH is added at 55° and the mixture heated for afurther 1/2 hr at this temperature and then cooled in an ice-bath andacidified with 1 ml conc. HCl. The solvent is evaporated and the residuepartitioned between 50 ml of CH₂ Cl₂ and 50 ml of water. The organicphase is concentrated to give a white solid, m.p. 71°-73°.

EXAMPLE 13 2-[(4,6-dimethoxy-2-pyrimidinyl)-α-iminomethyl]benzoic acid(Table C, cpd. no. 51)

2.67 g of isopropyl 2-bromobenzoate are dissolved in 100 ml of drydiethylether, the solution cooled to -100° C. and 6.6 ml of 1.6Mn-butyllithium solution added. Stirring is continued for 10 min and 12 gof 2-cyano-4,6-dimethoxypyrimidine in 60 ml of diethylether is addedover 2 min at -100° C. The mixture is stirred for 1/2 hr at -80° andthen allowed to warm to RT. 3 g of NH₄ Cl in 30 ml of water is added tothe reaction mixture, cooled in an ice-bath. The ether layer isseparated off, washed with water (2×30 ml) and concentrated. The gummyresidue is dissolved in 20 ml of 85/15 hexane/ethyl acetate, and CH₂Cl₂, and flash chromatographed on silica gel using 800 ml 85/15hexane/ethyl acetate, 500 ml 1% methanol in ethyl acetate, 500 ml 5%methanol in ethyl acetate and 500 ml of 80/20 acetone/methanol (40fractions at 50 ml; 1 at 200 ml). Fractions 7 to 10 yielded titlecompound which on recrystallization from CH₂ Cl₂ melted at 225°-235° C.

EXAMPLE 245--Chloro-5-(4,6-dimethoxy-2-pyrimidinyl)furo[3,4-b]pyridine-7(5H)-one(Table B, cpd. no. 68)

A mixture of 490 mg of5-(4,6-dimethoxy-2-pyrimidinyl)furo[3,4,b]pyridine-7(5H)one and 50 ml ofmethanol is heated at 55° for 1/2 hour or until a homogenous solution isformed. 2.6 g of NaOCl (common house bleach) is added dropwise. Themixture is taken up in dichloromethane an the organic phase separatedand evaporated to dryness to yield the title compound, mp 146°-148° C.

EXAMPLE 153-[(4,6-dimethoxy-2-pyrimidinyl)carbonyl]-pyridine-2-carboxylic acid(Table E, cpd. no. 63)

0.208 g of 50% NaOH is added at 55° to a solution of 0.551 g of5-chloro-5-(4,6-dimethoxy-2-pyrimidinyl)-furo[3,4,b]pyridine (Table B,cpd. no. 68) in 50 ml methanol. The mixture stirred for a further 1/2 hrat 55°, cooled in an ice-bath, acidified with 1 ml of concentrated HCland the solvent evaporated. The residue is partitioned between 50 ml ofCH₂ Cl₂ and 50 ml H₂ O and the CH₂ Cl₂ layer concentrated to give 0.39 gof the title product as a white solid, m.p. 71°-73° C.

EXAMPLE 162-(2-(4,4-dimethyl-oxazolin-2-yl)-benzyl)-4,6-dichloropyrimidine (TableC, cpd. no. 61)

To a mixture of 1.25 g of 2-o-tolyl-4,4-dimethyl-oxazoline in 20 ml ofether under N₂ atmosphere at -30° C. is added by syringe 4.2 ml of 1.6Mn-butyllithium in hexane with stirring which is continued for 1 hr at-10° C. 0.98 g of 4,6-dichloropyrimidine in 20 ml of ether are addedslowly to the reaction mixture which is then stirred at -45° to -30° C.for 30 min and at 0° C. for a further 30 min. The reaction mixture isquenched with acetic acid (0.4 ml) and water (0.1 ml) in THF (1.3 ml)and then treated with 1.5 g of 2,3-dichloro-5,6-dicyanobenzoquinone(DDQ) in 6 ml of THF. The temperature is brought to RT and the mixturestirred for 5 min after cooling to 0° C. 7.6 ml of 1 N NaOH (cooled) areadded and the mixture stirred for 5 min. The organic phase is separatedand dried over Na₂ SO₄ filtered and the solvent removed. Followingchromatography (10/90 ether/hexane) the title product is obtained.

EXAMPLE 172-(2-(4,4-dimethyl-oxazolin-2-yl)-benzyl)-4,6-dimethoxypyrimidine (TableC, cpd. no. 48)

To a solution of 1.7 g of2(2-(4,4-dimethyl-oxazolin-2-yl)-benzyl)-4,6-dichloropyrimidine in 100ml of methanol are added 2.18 g of 25% methanolic NaOCH₃ and the mixtureheated for 10 hrs at 65° C. with stirring. The temperature is lowered to60° and stirring continued overnight. The solvent is stripped and theresidue taken up in 80 ml of toluene and 50 ml of water. The toluenelayer was separated and washed with 50 ml of water, separated andconcentrated to give the title compound as a yellow oil.

EXAMPLE 182-(2-(4,4-dimethyl-oxazolin-2-yl)-α-bromobenzyl)-4,6-dimethoxypyrimidine (Table C, cpd. no. 62)

0.55 g of2-(2-(4,4-dimethyl-oxazolin-2-yl)-benzyl)-4,6-dimethoxypyrimidine, 0.30g of a N-bromosuccinimide, 0.03 g of benzoyl peroxide are dissolved in60 ml of CCl₄ and heated under reflux overnight at 75° C. The reactionmixture is filtered and the filtrate washed with 5% NaHCO₃ solution (50ml), 50 ml of water and the organic phase separated and concentrated togive the title compound.

EXAMPLE 192-(2-(4,4-dimethyl-oxazolin-2-yl)-benzoyl)4,6-dimethoxypyrimidine (TableC, cpd. no. 49)

A mixture of 1.2 g of2-(2-(4,4-dimethyl-oxazolin-2-yl)-α-bromobenzyl)-4,6-dimethoxy-pyrimidineand 2 g of Na₂ CO₃ in 30 ml of DMSO is heated with stirring at 50°-60°C. for 3 hrs. The mixture is poured into 150 ml of water and extractedwith toluene. The toluene extract is washed twice with water (2×50 ml)separated and concentrated. The thus obtained gum is chromatographedwith 800 ml of 80/20 hexane/ethyl acetate, 500 ml 70/30 hexane/ethylacetate, 60/40 ml hexane/ethyl acetate (50 ml fractions) fractions 29 to34 yielded the title compound.

EXAMPLE 20 2-chloro-6-(4,6-dimethoxy-2-pyrimidinylcarbonyl)-benzoic aciddimethylamide (Table C, cpd. no. 57)

1.0 g of 7-chloro-3-cyano-3-(4,6-dimethoxy-2-pyrimidinyl) phthalide isdissolved in 15 ml of THF. 0.7 ml of a 40% aqueous dimethylaminesolution is then added via syringe whereupon the solution darkens.Stirring is continued at R.T. for 15 minutes and the mixture dilutedwith water and partitioned between ethyl acetate and water. The organicphase is separated, washed with 2N H₂ SO₄, then brine, dried andconcentrated. The residue is purified on silica gel, eluant 200 ml of50% ethyl acetate/hexane then 100% ethyl acetate. Fractions 12 to 15yielded the title compound, m.p. 141°-142° C.

EXAMPLE 21 3-acetoxy-7-chloro-3-(4,6-dimethyloxy-2-pyrimidinyl)phthalide(Table A, cpd. no. 125)

1.1 g of 7-chloro-3-(4,6-dimethoxy-2-pyrimidinyl)-3-hydroxy-phthalide isdissolved in 20 ml of pyridine and 0.3 ml of acetic anhydride added withstirring. After stirring for 20 min the mixture is poured into 2N HCland extracted with two portions of ethyl acetate. The combined ethylacetate extracts are washed once with 2N HCl, once with H₂ O and oncewith brine and dried over magnesium sulfate. Filtration and evaporationproduced the title compound as a white solid, m.p. 213°-215°.

EXAMPLE 223-[(4,6-dimethoxy-α-hydroxy-2-pyrimidinyl)methyl]pyridine-2-carboxamide(Table E, cpd. no. 82)

To a solution of 0.9 g of ammonia, in 15 ml of methanol, is added 0.5 gof 3[(4,6-dimethoxy-2-pyrimidinyl)-7-azaphthalide. After stirring for 2hrs at RT, the methanol is removed under reduced pressure and theconcentrate recrystallized from toluene to give the title compound as awhite solid, m.p. 135°-137° C.

EXAMPLE 233[(4,6-dimethoxy-2-hydroxy-2-pyrimidinyl)methyl]pyridine-2-[carboxy-(4-isopropyl)anilide](Table E, cpd. no. 183)

To a solution of 3 ml of 4-isopropylaniline in 50 ml of toluene issyringed in 4 ml of 15.6% trimethylaluminum in hexane at RT. The mixtureis stirred for 0.5 hr at RT and 0.5 g of3-[(4,6-dimethoxy-2-pyrimidinyl)-7-azaphthalide is added. The mixture isstirred for 2 hrs at RT and acidified with 30 ml of 10% hydrochloricacid at 5°-10° C. The toluene solution is separated, washed with 20 mlof 10% hydrochloric acid, 20 ml of 5% sodium carbonate and 20 ml ofwater, dried and concentrated. The concentrate is recrystallized fromhexane to yield the title compound as a white solid, m.p. 113°-114° C.

3-[(4,6-dimethoxy-α-(ethoxycarbonyloxy)-2-pyrimidinyl)methyl]-pyridine-2-carboxamide(Table E, cpd. no. 129)

To a solution of 0.5 g of3-[(4,6-dimethoxy-α-hydroxy-2-pyrimidinyl)methyl]pyridine-2-carboxamide,0.05 g of 4-(dimethylamino)pyridine, and 1 ml of triethylamine, in 20 mlof toluene and 10 ml of dichloromethane is added 1 ml of ethylchloroformate at RT. After stirring for 1 hr at ambient temperature, themixture is washed with water (2×30 ml), dried and concentrated on arotoevaporator. The concentrate is digested with 1/1 mixture ofhexane-toluene, 10 ml, at 50° C., cooled to RT and filtered to isolate0.45 g of the title compound as a yellow solid, m.p. 112°-114° C.

EXAMPLE 253-[(4,6-dimethoxy-α-benzoyloxy-2-pyrimidinyl)methyl]pyridine-2-(N,N-dibenzoyl)carboxamide(Table E, cpd. no. 159)

To a solution of 0.05 g of3-[(4,6-dimethoxy-α-hydroxy-2pyrimidinyl)methyl]-2-carboxamide, 0.5 g,4-(dimethylamino)pyridine and 4 ml of triethylamine in 30 ml ofdichloromethane is added 1.4 g of benzoyl chloride at RT in twoportions. The reaction mixture is stirred at RT for 17 hrs and washedwith 30 ml of water, 30 ml of 5% hydrochloric acid and 30 ml of water.The dichloromethane solution is concentrated and the concentrate flashchromatographed through 300 ml silica gel, 230-400 mesh, using 1 L 70/30hexane-ethyl acetic and 500 ml 50/50 hexane-ethyl acetate as elutingsolvent mixtures. Fractions 18-21 gave after recrystallization from70/30 hexane ethyl acetate the title compound as a white solid, m.p.168°-170° C.

EXAMPLE 263-[(4,6-dimethoxy-α-(N-methylcarbamoyloxy)-2-pyrimidinyl)methyl]-2-pyridinecarbox(N-allyl)amide (Table E, cpd. no. 133)

To a solution of 0.5 g of3-[(4,6-dimethoxy-α-hydroxy-2-pyrimidinyl)methyl]-2-pyridinecarbox(N-allyl)amide and 3 drops of triethylamine, in 20 ml ofdichloromethane is added 3 ml of methyl isocyante, in three 1 mlportion/day while stirring at RT for 3 days. The reaction mixture iswashed with water (2×50 ml), dried and concentrated. The concentrate isflash chromoatographed through 300 ml silica gel, 230-400 mesh, using 1L 50/50 hexane-ethyl acetate, 500 ml ethyl acetate, 500 ml 80/20 ethylacetate methanol taking 34 fractions (50 m/m). Fractions 21-25 give 0.4g of the title product as a yellow gum.

EXAMPLE 27 Preparation of ethyl2-bromo-4-[(4,6-dimethoxy-2-pyrimidinyl)methyl]nicotinate (Table D, cpd.no. 523)

7.32 g of ethyl 2-bromo-4-methyl nicotinate and 150 ml of THF are cooledin a dry ice/acetone bath under N₂ atmosphere, 30 ml of LDA are addedover 5 mins and the mixture stirred for 30 mins. 6.55 g of2-methylsulphonyl-4,6-dimethoxypyrimidine are added as a solid, rinsingwith 50 ml of THF, and the mixture stirred cold for 2 hrs and slowlyallowed to warm. The THF is evaporated, ca 75 ml of water added and themixture extracted three times with methylene dichloride. The combinedextracts are evaporated and the residue taken up with 20 ml of 25% ethylacetate/hexane and flash chromatographed using 2 l of 25% ethylacetate/hexane in 50 ml fractions. Fractions 7 to 14 are combined,evaporated and placed in a Kugelrohr at ca 105° for 2 hrs. The residueis taken up in 20 ml of 10% ethyl acetate/hexane and flashchromatographed with 2 l 10% ethyl acetate/hexane in 50 ml portions toyield title compound (NMR) in fractions 18 to 32.

EXAMPLE 28 Preparation ofethyl-2-bromo-4-[(4,6-dimethoxy-2-pyrimidinyl)carbonyl]nicotinate (TableD, cpd. no. 524)

3.28 g of ethyl2-bromo-4-[(4,6-dimethoxy-2-pyrimidinyl)methyl]nicotinate, 3.61 g ofSeO₂ and 100 ml of glacial acetic acid are combined under nitrogen,heated to 110° for 1.5 hrs and slowly cooled to RT still under nitrogen.The mixture is filtered, washed through with 10 ml of acetic acid andthe filtrate evaporated to remove the acetic acid. 100 ml of methylenedichloride is added to the residue and the mixture washed twice with 100ml of sat. aqueous NaHCO₃. The CH₂ Cl₂ phase is filtered and evaporatedand the residue digested with 25 ml of 25% ethyl acetate/hexane at 50°for 15 mins. This solution is then poured onto a silica gel column andeluted with 3×125 ml of 25% ethyl acetate/hexane. Evaporation ofcombined fractions 1 and 2 yields the title product mp 98°-99°.

EXAMPLE 29 Preparation of1-(4,6-dimethoxy-2-pyrimidinyl)-l-hydroxy-4-methyl-furo[3,4-c]pyridine-3(1H)-one(Table B, cpd. no. 260)

0.37 g of ethyl2-methyl-4-[4,6-dimethoxy-2-pyrimidinyl)methyl]nicotinate, 0.37 g ofpotassium permanganate and 100 ml of water are combined and heated atreflux for 45 mins. The mixture is cooled, a further 0.185 g ofpermangante added and refluxing resumed for 45 mins. The mixture iscooled to RT, filtered through celite, and sodium sulfite added untilthe aqueous layer becomes colorless. The filtrate is once againfiltered, washed with water and extracted with 4×75 ml of methylenechloride. The combined extracts are evaporated, the residue taken up in50 ml of warm ethyl acetate and poured onto a silica column and elutedwith 2×100 ml of ethyl acetate. The combined fractions are evaporated toyield title product mp 203°-204°.

EXAMPLE 30 Preparation of N-methyl3-phenyl-5-(4,6-dimethoxy-2-pyrimidinyl-α-t-butoxymethyl)-4-isoxazolecarboxanilide(Table F, cpd. no. 412)

To a solution of 1.29 g of N-methyl3-phenyl-5-(4,6-dimethoxy-2-pyrimidinylmethyl)-4-isoxazolecarboxanilide,in 60 ml of THF is syringed in 2 ml of 1.5 molar n-butyl lithium inhexane at -70° C. The mixture is stirred for 10 mins at -70° C. and 0.6g of t-butylperoxybenzoate, in 10 ml of THF, added over 10 mins. Thereaction mixture is stirred at -70° C. for 1 hr and allowed to warm toRT. The mixture is diluted with 300 ml of water and extracted with 2×30ml of toluene. The toluene solution is dried, concentrated and theconcentrate flash chromatographed through 300 ml of silica gel, 230-400mesh, using 1 l of 70/30 hexane/ethyl acetate, 500 ml of 50/50hexane/ethyl acetate taking 30×50 ml fractions. Fractions 11-14 give thetitle compound as a yellow gum.

EXAMPLE 31 Preparation of N-methyl3-phenyl-5-(4,6-dimethoxy-2-pyrimidinyl-α-hydroxymethyl)-4-isoxazolecarboxanilide(Table F, cpd. no. 424)

A mixture of 0.6 g of N-methyl3-phenyl-5-(4,6-dimethoxy-2-pyrimidinyl-α-t-butoxymethyl)-4-isoxazolecarboxanilide,and 4 drops of borontrifluoridemethanol complex in 50 ml of toluene isheated at 50°-55° C. for 2 hours, washed with 20 ml of water, 50 ml of5% sodium bicarbonate solution, dried and concentrated. The concentrateis recrystallized from hexane/methylene dichloride to give a whitesolid, mp 130°-131° C.

EXAMPLE 32 Preparation of N-methyl3-phenyl-5-(4,6-dimethoxy-2-pyrimidinylcarbonyl)-4-isoxazolecarboxanilide(Table F, cpd. no. 429)

To a solution of 1.5 ml of oxalyl chloride in 30 ml ofmethylenedichloride cooled to -60° C. is added a solution of 2 ml ofDMSO in 10 ml of methylene dichloride dropwise at -60° C. After 2 mins asolution of 0.6 g of N-methyl3-phenyl-5-(4,6-dimethoxy-2-pyrimidinyl-α-hydroxymethyl)-4-isoxazolecarboxanilidein 10 ml of methylene dichloride is added over 3 mins at -60° C. Themixture is stirred for 15 mins at -60° C. and 1 ml of triethylamineadded. The mixture is allowed to warm to RT, washed with water (3×30ml), dried and concentrated. The concentrate is flash chromatographedthrough 300 ml silica gel, 230-400 mesh, using 1 l 60/40 hexane/ethylacetate, 500 ml 50/50 hexane/ethyl acetate taking 25×50 ml fractions.Fractions 11-14 give the desired product, a yellow gum.

EXAMPLE 33 Preparation of N-methyl3-phenyl-5-(4,6-dimethoxy-2-pyrimidinylcarbonyl)-4-isoxazolecarboxanilide(Table F, cpd. no. 429, alternative method)

A solution of 100 mg of N-methyl3-phenyl-5-(4,6-dimethoxy-2-pyrimidinylmethyl)-4-isoxazolecarboxanilide,20 mg of dicobalt octacarbonyl, and 1 ml of t-butylhydroperoxide, in 60ml of acetonitrile is refluxed for 48 hours. An additional 1 ml oft-butylhydroperoxide is added after 12 hrs and 24 hrs. Thin layerchromatography after 48 hrs indicates the presence of starting materialand the title compound.

EXAMPLE 34 Oxidation of N-methyl3-(4,6-dimethoxy-2-pyrimidinylmethyl)-5-trimethylsilyl-4-isothiazolecarboxanilide

A mixture of 2.0 g of N-methyl3-(4,6-dimethoxy-2-pyrimidinylmethyl)-5-trimethylsilyl-4-isothiazolecarboxanilide,1.5 g of manganese (III) triacetate, 20 ml of acetic acid and 30 ml ofmethylene dichloride is stirred at RT for 48 hours. The resultingsuspension is suction filtered through filter aid and the filter cakewashed with water and methylene dichloride. The organic layer isseparated, dried and concentrated. The concentrate is flashchromatographed through 300 ml silica gel, 230-400 mesh, using 1 l 70/30hexane/ethyl acetate, 500 ml 50/50 hexane/ethyl acetate taking 30×50 mlfractions. Fractions 10-15 give a mixture of two components which isheated with boron trifluoride methanol complex (4 drops) in 50 ml oftoluene at 80° C. for 2 hrs. The reaction mixture is washed with 30 mlof 15% sodium bicarbonate solution, dried, and concentrated. Theconcentrate is flash chromatographed through 300 ml silica gel, 230-400mesh, using 1 l 60/40 hexane/ethyl acetate, 500 ml 40/60 hexane/ethylacetate and 200 ml ethyl acetate taking 34×50 ml fractions. Fractions20-23 give N-methyl3-(4,6-dimethoxy-2-pyrimidinylmethyl)-4-isothiazolecarboxanilide, 0.12g, mp 92°-93° (Table F, cpd. no. 513). Fractions 24-28 give N-methyl3-(4,6-dimethoxy-2-pyrimidinylcarbonyl)-4-isothiazolecarboxanilide, 0.3g, mp 140°-142° C. (Table F, cpd. no. 514).

EXAMPLE 35 3-[(4,6-dimethoxy-2-pyrimidinyl)hydroxymethyl]-N-methyl-2-pyridine carboxamide (Table E, cpd. no. 108)

7.2 g of methylamine gas is bubbled into 300 ml of anhydrous methanolover 10 min at 10°, 30 g of5-(4,6-dimethoxy-2-pyridimidinyl)furo[3,4-b]pyrdine-7(5H)-one added andthe mixture stirred at RT for 14 hours. The reaction mixture is thenfiltered and the filtrate concentrated to ca 50 ml. The resultingsuspension is cooled to ca 10° and the precipitate filtered to isolatethe title compound m.p. 132°-133° C.

EXAMPLE 363-[(4,6-dimethoxy-2-pyrimidinyl)carbonyl]-2-pyridinecarboxylic acid(Table E, cpd. no. 64)

30.3 g of KMnO₄ and 32.3 g of NaHCO₃ are suspended in 700 ml of waterand 57 g of lithium3-[(4,6-dimethoxy-2-pyrimidinyl)hydroxymethyl]-2-pyridine carboxylate isadded with stirring. The reaction mixture is refluxed for 4 hrs andsuction filtered hot. The filtrate is cooled over ice water and audifiedwith conc. HCl (60 ml). The precipitated solid is filtered and dried invacuo at 50° to give the title compound m.p. 159°-161° C.

EXAMPLE 375-chloro-5-(4,6-dimethoxy-2-pyrimidinyl)furo[3,4-b]pyridine-7(5H)-one(Table B, cpd. no. 68)

45.53 g of3-[(4,6-dimethoxy-2-pyrimidinyl)carbonyl]-2-pyridinecarboxylic acid aresuspended in 700 ml of carbon tetrachloride and 186.4 g of thionylchloride added with stirring. The suspension is heated to 70° C. for 4hrs and the reaction mixture then cooled to RT and the excess thionylchloride and carbon tetrachloride evaporated off to give the titlecompound as a tan solid m.p. 146°-148° C.

EXAMPLE 383-[(4,6-dimethoxy-2-pyrimidinyl)carbonyl]-N,N-dimethyl-2-pyridinecarboxamid(Table E, cpd. no. 385)

15.8 g of anhydrous dimethylamine gas is bubbled into 36 g of5-chloro-5-(4,6-dimethoxy-2-pyrimidinyl)furo[3,4-b]pyridine-7(5H)-one in350 ml of methylene dichloride cooled in an ice bath and the mixturethen stirred overnight at RT. The reaction mixture is then washed withsaturated brine solution (3×50 ml) passed through phase separating paperand the filtrate concentrated. The concentrate is dissolved in methylenedichloride, charcoal treated at RT for 1 hr and filtered.

The filtrate is concentrated to 60 ml diluted with hexane, digested for1 hr at 35° and allowed to crystallize overnight at RT. The precipitateis filtered to isolate 35.15 g of the title product m.p. 124°-126° C.

EXAMPLE 39 3-cyano-4,7-dichloro-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide(Table A, cpd. no. 269)

21.5 g of NaH in oil dispersion are added to 112.75 g of3-cyano-4,7-dichlorophthalide and 96.7 g of4,6-diemthoxy-2-methylsulfonyl-pyrimidine. (The hydride is washed withhexane, the hexane removed by suction and the residue covered with DMFand cooled in an ice bath.) The reaction mixture is left to stirovernight at RT and the solution then poured into 3L of water containing15 ml of conc. H₂ SO₄ and stirred mechanically until a viscous gumformed around the stirred blade. The water layer is decanted andextracted with 3×400 ml of toluene, the first two extracts added to thegum and the mixture stirred until the gum dissolved. The toluenesolution is washed 2×100 ml of water and 1×100 ml of toluene and thecombined toluene layers dried over Na₂ SO₄ concentrated to 400 ml andleft to stand overnight. The still homogeneous solution isflash-chromatographed over silica gel with toluene (250 ml fraction 5)fractions 5-9 are combined and stripped to give 30 g of the titleproduct m.p. 123°-126° C.

EXAMPLE 404,7-dichloro-3-(4,6-dimethoxy-2-pyrimidinyl)-3-hydroxyphthalide (TableA, cpd. no. 250)

70 g of 3-cyano-4,7-dichloro-3-(4,6-dimethoxy-2-pyrimidinyl)phthalideare slurried in 100 ml of methanol and 16 g of NaOH pellets with 125 mlof water added. The mixture is stirred and heated to reflux for 30mins., the solution cooled and the methanol stripped. The aqueoussolution was diluted with 400 ml of water, washed with 100 ml of etherand then added dropwise to 400 ml of 1 NH₂ SO₄ to give a solid which isfiltered and dried in vacuum for 1 hr at 60°. The solid is trituratedwith 100 ml of ether and the suspension left overnight at RT and thesolid isolated by filtration to give the title product m.p. 161°-175° C.

EXAMPLE 41 3,6-dichloro-2-[(4,6-dimethoxy-2-pyrimidinyl)carbonyl]benzoicacid, isopropylammonium salt (Table C, cpd. no. 481)

24.13 g of4,7-dichloro-3-(4,6-dimethoxy-2-pyrimidinyl)-3-hydroxyphthalide isslurried in 500 ml of methylene dichloride and 200 ml of methanol and125 ml of freshly distilled isopropylamine added. The mixture is heatedto reflux and the solution filtered, cooled and stripped. The solid isdried in vacuum for 4 hrs at 45° C. to give the title product m.p.194°-196° C.

EXAMPLE 424,7-dichloro-3-(4,6-dimethoxy-2-pyrimidinyl)-3-hexanoyloxyphthalide(Table A, cpd. no. 265)

52 g of 4,7-dichloro-3-(4,6-dimethoxy-2-pyrimidinyl)-3-hydroxyphthalideand 500 ml of methylene dichloride are cooled in an ice bath and 23 mlof triethylamine and 1.1 g of DMAP added. The mixture is stirred untilmost of the solid dissolves, 35.2 g of freshly distilled hexanoicanhydride are added and the mixture is stirred for 48 hrs under N₂ atRT. The solution is washed with 2×100 ml 1 NH₂ SO₄, 1×100 ml 0.1N NaOHand brine dried over Na₂ SO₄ and concentrated to give 58.2 g of crudeproduct which is triturated with 150 ml of ether and filtered to isolatethe title product m.p. 103°-105° C.

The following compounds may be prepared analogously to the precedingexamples or as otherwise described herein. Unless otherwise stated alkylgroups are straight chained i.e. in "n"-form.

    TABLE A      ##STR33##                 melting point Cpd No Y.sub.1 Y.sub.2 Y.sub.3 Y W.sub.1     W.sub.2 W.sub. 3 W.sub.4 R.sub.1 (°C.)       1 H H H OH N CH COCH.sub.3 N OCH.sub.3 136-138 2 H H H H N CH COCH.sub.     3 N OCH.sub.3 102-104      3 H H H     ##STR34##      N CBr COCH.sub.3 N OCH.sub.3 215-225  4 H H H H N CBr CH N OCH.sub.3     136-138 5 H H 5-Cl H N CH COCH.sub.3 N OCH.sub.3 151-153 6 7-Cl H H H N     CH COCH.sub.3 N OCH.sub.3 148-149 7 H 6-Cl H H N CH COCH.sub.3 N     OCH.sub.3 138-139 8 H H H H N CH CCl N OCH.sub.3 152-153 9 7-Cl H H H N     CH CCl N OCH.sub.3 128-130 10 H H 4-Cl H N CH COCH.sub.3 N OCH.sub.3     98-99 11 7-CH.sub.3 H H H N CH COCH.sub.3 N OCH.sub.3 138-140 12 H H H H     N CH CCl N CH.sub.3 133-135 13 7-Cl H H OH N CH COCH.sub.3 N OCH.sub.3     188-190 14 7-Cl H H H N CH COiC.sub.3 H.sub.7 N OCH.sub.3 101-102 15     7-OCH.sub.3 H 4-Br H N CH COCH.sub.3 N OCH.sub.3 126-128 16 7-Cl H H H N     CH COCH.sub.2 CF.sub.3 N OCH.sub.3 112-113      17 7-Cl H H H N CH COCH.sub.3 N      ##STR35##      136-138      18 7-Cl H H H N CH     ##STR36##      N OCH.sub.3 115-116      19 7-Cl H H H N CH COCH.sub.3 N     ##STR37##      85-88  20 7-Cl H H H N CH COCH.sub.3 N OC.sub.2 H.sub.5 98-100 21 7-Cl     H H Cl N CH COCH.sub.3 N OCH.sub.3 163-165 22 7-Cl H H H N CH COCH.sub.2     CCCH.sub. 3 N OCH.sub.3 131-133 23 7-Cl H H SCH.sub.3 N CH COCH.sub.2     CCCH.sub.3 N OCH.sub.3 134-136 24 7-Cl H H H N CH COCH.sub.3 N OCH.sub.2     CHCH.sub.2 72-75 25 7-Cl H H H N N COCH.sub.3 N OCH.sub.3 157-160 26     7-OCH.sub.3 H H H N CH COCH.sub.3 N OCH.sub.3 152-154 27 7-Cl H H CN N     CH COCH.sub.3 N OCH.sub.3 159-161 28 7-Cl H H CN N N COCH.sub.3 N     OCH.sub.3 184-186 29 7-Cl 6-Cl H H N CH COCH.sub.3 N OCH.sub.3 194-195     30 7-Cl H H OCH.sub.3 N CH COCH.sub.3 N OCH.sub.3 180-183      31     ##STR38##      H H CN N CH COCH.sub.3 N OCH.sub.3 169-171  32 7-OCH.sub.3 6-OCH.sub.3     H      ##STR39##      N N COCH.sub.3 N OCH.sub. 3 134-136  33 7-Cl H H H N CH CCH.sub.3 N     CH.sub.3 164-166      34 H H H     ##STR40##      N CBr CH N OCH.sub.3 163-176  35 H 5-Cl H "H1" N CH COCH.sub.3 N     OCH.sub.3 151-153 36 7-Cl H H "H2" N N COCH.sub.3 N OCH.sub.3 126-127 37     H H H OH N CCl COCH.sub.3 N OCH.sub.3 162-165 38 7-F H H CN N CH     COCH.sub.3 N OCH.sub.3 132-134 69 7-Cl H H OC.sub.2 H.sub.5 N CH     COCH.sub.3 N OCH.sub.3 148-151 72 7-OCH.sub.3 H H CN N CH COCH.sub.3 N     OCH.sub.3 159-163 73 H H H CH.sub.3 N CH COCH.sub.3 N OCH.sub.3 87-89 75     H H H "H1" N CH COCH.sub.3 N OCH.sub.3 168-170  88 7-Cl H H H N CH      ##STR41##      N OCH.sub.3 gum, NMR      98 7-Cl H H H N CH     ##STR42##      N OCH.sub.3 97-98      101 7-Cl H H H N CH     ##STR43##      N H 125-127      102 7-Cl H H H N CH     ##STR44##      N H 83-85      104     ##STR45##      H H CN N CH COCH.sub.3 N OCH.sub.3 105-108      105     ##STR46##      H H OH N CH COCH.sub.3 N OCH.sub.3 109-110  109 7-F H H OCH.sub.3 N CH  O     CCH.sub.3 N OCH.sub.3 172-173.5 113 7-F H H H N CH COCH.sub.3 N OCH.sub.3      138-140 117 7-F H H OH N CH COCH.sub.3 N OCH.sub.3 183.5-185.5 118 7-OH     H H CN N CH COCH.sub.3 N OCH.sub.3 121-122      120     ##STR47##      H H CN N CH COCH.sub.3 N OCH.sub.3 174-176  125 7-Cl H H acetoxy N CH     COCH.sub.3 N OCH.sub.3 213-215 134 7-OH H H OH N CH COCH.sub.3 N     OCH.sub.3 138-141           (decomp) 135 7CH.sub.3 SO.sub.2 O H H CN N     CH COCH.sub.3 N OCH.sub.3 159-161 137 7-OCON(C.sub.2 H.sub.5).sub.2 H H     CN N CH COCH.sub.3 N OCH.sub.3 123-125 138 7propargyloxy H H CN N CH     COCH.sub.3 N OCH.sub.3 174-175      139     ##STR48##      H H CN N CH COCH.sub.3 N OCH.sub.3 170-171      140     ##STR49##      H H CN N CH COCH.sub.3 N OCH.sub.3 169-172      145     ##STR50##      H H H N CH COCH.sub.3 N OCH.sub.3 108-110      146     ##STR51##      H H H N CH COCH.sub.3 N OCH.sub.3 115-118  147 7-OCH.sub.3 H H OH N CH  O     CCH.sub.3 N OCH.sub.3 174-176 153 7propargyloxy H H H N CH COCH.sub.3 N     OCH.sub.3 130-131      154     ##STR52##      H H CN N CH COCH.sub.3 N OCH.sub.3 182-185(decomp)  166 7-OCF.sub.3 H H     OH N CH COCH.sub.3 N OCH.sub.3 131-132 167 7-OCH.sub.3 H H acetoxy N CH  O     CCH.sub.3 N OCH.sub.3 201-202      180     ##STR53##      H H H N CH COCH.sub.3 N OCH.sub.3 133-136  190 7-Oallyl H H H N CH     COCH.sub.3 N OCH.sub.3 109-110 195 7-CF.sub.3 O H H acetoxy N CH     COCH.sub.3 N OCH.sub.3 165-166      203 7-Cl H H     ##STR54##      N CH COCH.sub.3 N OCH.sub.3 178-180      204 7-Cl H H     ##STR55##      N CH COCH.sub.3 N OCH.sub.3 131-133      205 7-Cl H H     ##STR56##      N CH COCH.sub.3 N OCH.sub.3 177-179  208 7-Cl H H benzoyloxy N CH     COCH.sub.3 N OCH.sub.3 192-194      240 7-Cl H H     ##STR57##      N CH COCH.sub.3 N OCH.sub.3 158-160  250 7-Cl H 4Cl OH N CH COCH.sub.3     N OCH.sub.3 171-175 253 7-Cl H H cinnamoyloxy N CH COCH.sub.3 N OCH.sub.3      221-224      256 7-Cl H H     ##STR58##      N CH COCH.sub.3 N OCH.sub.3 102-103  258 7-Cl H H 2-butenoxy N CH     COCH.sub.3 N OCH.sub.3 102-103      263 7-Cl H 4-Cl     ##STR59##      N CH COCH.sub.3 N OCH.sub.3 163-164      265 7-Cl H 4-Cl     ##STR60##      N CH COCH.sub.3 N OCH.sub.3 87-91      266 7-Cl H 4-Cl     ##STR61##      N CH COCH.sub.3 N OCH.sub.3 137-138      267 7-Cl H 4-Cl     ##STR62##      N CH COCH.sub.3 N OCH.sub.3 128-131  268 7-F H 4-F CN N CH COCH.sub.3 N O     CH.sub.3 135-136 269 7-Cl H 4-Cl CN N CH COCH.sub.3 N OCH.sub.3 123-126     270 7-Cl H 4-Cl H N CH COCH.sub.3 N OCH.sub.3 156-161 307 4-Cl H H OH N     CH COCH.sub.3 N OCH.sub.3 146-150 319 4-Cl H H CN N CH COCH.sub.3 N     OCH.sub.3 132-133 320 4-Cl H H OCH.sub.3 N CH COCH.sub.3 N  OCH.sub.3     168-168.5      326 7-Cl H H     ##STR63##      N CH COCH.sub.3 N OCH.sub.3 142-143      409 7-Cl H H     ##STR64##      N CH COCH.sub.3 N OCH.sub.3 162-163  452 7-Cl 4-Cl H OCH.sub.2      CHCH.sub.2 N CH COCH.sub.3 N OCH.sub.3 135-136 459 7-OCH.sub.3 4-Cl H     OH N CH COCH.sub.3 N OCH.sub.3 212-213 476 7-Si(CH.sub.3).sub.3 H H OH N     CH COCH.sub.3 N OCH.sub.3 103-104 477 7-OCH.sub.3 4-Cl H H N CH COCH.sub.     3 N OCH.sub.3 183-185 486 7-Cl 4-Cl H Cl N CH COCH.sub.3 N OCH.sub.3     139-142 526 7-Cl 4-F H OH N CH COCH.sub.3 N OCH.sub.3 178-179  543 7-Cl     4-CH.sub.3 H      ##STR65##      N CH COCH.sub.3 N OCH.sub.3 95-96      549 7-Cl 4-OCH.sub.3 H     ##STR66##      N CH COCH.sub.3 N OCH.sub.3 116-117      568 7-Cl 4-Cl H CN N CCl COCH.sub.3 N OCH.sub.3 188.5-189      580 7-CH.sub.3 4-F H      ##STR67##      N CH COCH.sub.3 N OCH.sub.3 103-104.5  582 7-CH.sub.3 4-F H H N CH     COCH.sub.3 N OCH.sub.3 138-140  588 7-SO.sub.2      CH.sub.3 H H     ##STR68##      N CH COCH.sub.3 N OCH.sub.3 146-148      590 7-Cl 4-Cl H     ##STR69##      N CH COCH.sub.3 N OCH.sub.3 145-148      591 7-Cl 4-Cl H     ##STR70##      N CH COCH.sub.3 N OCH.sub.3 130-132      595 7-Cl 4-Cl H     ##STR71##      N CH COCH.sub.3 N OCH.sub.3 127-129  597 7-Cl 4-NO.sub.2 H CN N CH     COCH.sub.3 N OCH.sub.3 151.5-152.5      599 7-Cl 4-Cl H     ##STR72##      N CH COCH.sub.3 N OCH.sub.3 171-174      605 7-Cl 4-Cl H     ##STR73##      N CH COCH.sub.3 N OCH.sub.3 81-83      606 7-Cl 4-Cl H     ##STR74##      N CH COCH.sub.3 N OCH.sub.3 103-108      607 7-Cl 4-Cl H     ##STR75##      N CH COCH.sub.3 N OCH.sub.3 98-101      608 7-Cl 4-Cl H     ##STR76##      N CH COCH.sub.3 N OCH.sub.3 83-85      610 7-CH.sub.3 4-Cl H     ##STR77##      N CH COCH.sub.3 N OCH.sub.3 114-115      611 7-Cl 5-Cl H     ##STR78##      N CH COCH.sub.3 N OCH.sub.3 206-210      612 7-Cl 4-F H     ##STR79##      N CH COCH.sub.3 N OCH.sub.3 122-123      615 7-Br H H     ##STR80##      N CH COCH.sub.3 N OCH.sub.3 142-144      618 7-CN H H     ##STR81##      N CH COCH.sub.3 N OCH.sub.3 160-162  623 7-Cl 4-Cl H OCH.sub.3 N CH     COCH.sub.3 N OCH.sub.3 184-185 624 7-Cl 4-CH.sub.3 H OCH.sub.3 N CH     COCH.sub.3 N OCH.sub.3 178-179

    TABLE B      ##STR82##                  melting point Cpd No W.sub.7 W.sub.8 W.sub.9 W.sub.10 Y     W.sub.1 W.sub.2 W.sub.3 W.sub.4 R.sub.1 (°C.)       39 CH CH CH N H N CH C OCH.sub.3 N OCH.sub.3 149-151 40 N CH CH CH H N     CH COCH.sub.3 N OCH.sub.3 167-168 41 CH CH N CH H N CH COCH.sub.3 N     OCH.sub.3 oil NMR 42 CH N CH CH H N CH COCH.sub.3 N OCH.sub.3 120-126 43     N CCl CH CH H N CH COCH.sub.3 N OCH.sub.3 166-169 44 N CH CC.sub.2     H.sub.5 CH H N N COCH.sub.3 N OCH.sub.3 oil NMR 45 N CH CH CH H N N     COCH.sub.3 N OCH.sub.3 75-80 46 CH CC.sub.2      H.sub.5 CH N H N CH COCH.sub.3 N OCH.sub.3 oil NMR 47 CH CH CH N     CH.sub.3 N CH COCH.sub.3 N OCH.sub.3 98-101 68 N CH CH CH Cl N CH     COCH.sub.3 N OCH.sub.3 146-148 70 N CH CH CH "H1" N CH COCH.sub.3 N     OCH.sub.3 173-176 89 CCH.sub.3 CH CH N H N CH C OCH.sub.3 N OCH.sub.3     129-131 92 N CH CH CH H N CH COCH.sub.2 CF.sub.3 N OCH.sub.3 116-119 93     N CH CH CH H N CH CCH.sub.3 N CH.sub.3 193-195 94 N CH CH CH H N CH CCl     N OCH.sub.3 147-149      95 N CH CH CH H N CH     ##STR83##      N OCH.sub.3 oil NMR  99 N CH CH CH H N CH COC.sub.3 H.sub.7 N OCH.sub.3     140-142 100 N CH CH CH H N CH COC.sub.2 H.sub.5 N OCH.sub.3 133-135 106     N CH CH CH H N CH COallyl N OCH.sub.3 112-114 107 N CH CH CH H N CH     COCH.sub.2      CCH.sub.3 N OCH.sub.3 oil NMR 114 CCl N CH CH H N CH COCH.sub.3 N     OCH.sub.3 168-170 121 COCH.sub.3 N CH CH H N CH COCH.sub.3 N OCH.sub.3     150-153            (decomp) 136 N CH CH CH H N CH COCH.sub.3 N H 158-160     141 N CH CH CH * N CH COCHF.sub.2 N OCHF.sub.2 145-147 148 CH CH CH N     "H1" N CH COCH.sub.3 N OCH.sub.3 212-213 175 CH CH CH N OH N CH COCH.sub.     3 N OCH.sub.3 172-178 260 CCH.sub.3 N CH CH OH N CH COCH.sub.3 N     OCH.sub.3 203-204 261 CCOOH N CH CH OH N CH COCH.sub.3 N OCH.sub.3     130-132            (decomp) 317 N CH CH CH H N CH COCH.sub.3 N CH.sub.3     138-140 408 N CH CH CH N(CH.sub.3)OCH.sub.3 N CH COCH.sub.3 N OCH.sub.3     168-170 572 N CH CH COCH.sub.3 CN N CH COCH.sub.3 N OCH.sub.3 177-179     629 N CH CH CH (1) N CH COCH.sub.3 N OCH.sub. 3 148-150 630 N CH CH CH     (2) N CH COCH.sub.3 N OCH.sub.3 155-159 631 N CH CH CH (3) N CH COCH.sub.     3 N OCH.sub.3 199-200 636 N CH CH CH (4) N CH COCH.sub.3 N OCH.sub.3     200-204 637 N CH CH CH (5) N CH COCH.sub.3 N OCH.sub.3 215-217     ##STR84##     ##STR85##

    TABLE C      ##STR86##                   melting point Cpd # Y.sub.1 Y.sub.2 Y.sub.3 R X Y W.sub.1     W.sub.2 W.sub.3 W.sub.4 R.sub.1 (°C.)                    48 H H H      ##STR87##      H H N CH C OCH.sub.3 N OCH.sub.3 oil NMR  49 H H H " O  N CH COCH.sub.3 N      OCH.sub.3 oil NMR                   50 H H H     ##STR88##      H H N CH COCH.sub.3 N OCH.sub.3 150-152  51 H H H COOH NH  N CH     COCH.sub.3 N OCH.sub.3 225-235             (free acid) 52 2-Cl H H CN H     H N CH COCH.sub.3 N OCH.sub.3 94-95 53 2-Cl H H COOH OH H N CH COCH.sub.3      N OCH.sub.3 153-157             (Li.sup.+  salt)               54 2-Cl     H H      ##STR89##       OCH.sub.3 N CH COCH.sub.3 N OCH.sub.3 oil NMR  55 2-Cl H H COOCH.sub.3 O       N CH COCH.sub.3 N OCH.sub.3 110-111 56 2-Cl H H CONHCH.sub.3 OH H N CH C    O     CH.sub.3 N OCH.sub.3 130-132 57 2-Cl H H CON(CH.sub.3).sub.2 O  N CH     COCH.sub.3 N OCH.sub.3 141-142 58 2-Cl H H COOH O  N CH COCH.sub. 3 N     OCH.sub.3 276-278             (Na.sup.+  salt)               59 2-Cl H H      ##STR90##      OCH.sub.3 H N CH COCH.sub.3 N OCH.sub.3 148-150  60 H H H COOH OH H N     CH COCH.sub.3 N OCH.sub.3 185 (dec.)             (Li.sup.+  salt)  61 H     H H      ##STR91##      H H N CH CCl N Cl NMR  62 H H H " Br H N CH COCH.sub.3 N OCH.sub.3 71 H     H H COOH OH H1 N CH COCH.sub.3 N OCH.sub.3 74 H H H COOH OH CH.sub.3 N     CH COCH.sub.3 N OCH.sub.3 >250             (Li.sup.+  salt) 76 2-Cl H H     COOC.sub.2 H.sub.5 O  N CH COCH.sub.3 N OCH.sub.3 66-67 77 2Cl H H     COOallyl O  N CH COCH.sub.3 N OCH.sub.3 81-83 78 2Cl H H COObuten-3-yl O      N CH COCH.sub.3 N OCH.sub.3 48-50 79 2Cl H H COObenzyl O  N CH COCH.sub.     3 N OCH.sub.3 99-101                   80 2Cl H H     ##STR92##       OH N CH COCH.sub.3 N OCH.sub.3 99-101      81 2Cl H H     ##STR93##       OH N CH COCH.sub.3 N OCH.sub.3 153-154  85 2Cl H H  CON(C.sub.2     H.sub.5).sub.2 O  N CH COCH.sub.3 N OCH.sub.3 110-111 86 H H H COObenzyl O     H H N CH COCH.sub.3 N OCH.sub.3 oil NMR               87 2Cl H H      ##STR94##       OH N CH COCH.sub.3 N OCH.sub.3 161-163  96 2-Cl H H CON(C.sub.2     H.sub.5).sub.2 OH H N CH COCH.sub.3 N OCH.sub.3 74-80 103 2-Cl H H     CONCH.sub.3 (benzyl) O  N CH COCH.sub.3 N OCH.sub.3 105-107 115 2-F H H     COOCH.sub.3 O  N CH COCH.sub.3 N OCH.sub.3 101-104 116 2-F H H COOallyl     O  N CH COCH.sub.3 N OCH.sub.3 97-99 122 H H H COOallyl O  N CH COCH.sub.     3 N OCH.sub.3 92-93 123 2-Cl H H COO 2-methyl- O  N CH COCH.sub.3 N     OCH.sub.3 137-139     allyl 124 2-Cl H H COO-3-methyl- O  N CH COCH.sub.3      N OCH.sub.3 54-57     but-2-enyl 126 2-Cl H H COOpropargyl O  N CH     COCH.sub.3 N OCH.sub.3 138-140 143 2-Cl H H COObut-2-enyl O  N CH     COCH.sub.3 N OCH.sub.3 61-65 156 2-OCH.sub.3 H H COOCH.sub.3 O  N CH     COCH.sub.3 N OCH.sub.3 142-143 163 2-F H H COOH OH H N CH COCH.sub.3 N     OCH.sub.3 Li.sup.+  salt             220-240 (decomp)  165 2-OCH.sub.3 H H      COOallyl O  N CH COCH.sub.3 N OCH.sub.3 100-101               181      ##STR95##      H H COOH OH H N CH COCH.sub.3 N OCH.sub.3 Li.sup.+  salt158-159  191     2-OCF.sub.3 H H COOCH.sub.3 O  N CH COCH.sub.3 N OCH.sub.3 80-82     (decomp) 192 3-Cl H H COOH OH H N CH COCH.sub.3 N OCH.sub.3 Li.sup.+     salt             170-174 (decomp) 194 5-Cl H H COOH OH H N CH COCH.sub.3     N OCH.sub.3 Li.sup.+  salt             225-227 (decomp) 197 4-Cl H H     COOH OH H N CH COCH.sub.3 N OCH.sub.3 Li.sup.+  salt             195-198     (decomp) 202 2-pro- H H COOH OH H N CH COCH.sub.3 N OCH.sub.3 Li.sup.+     salt  pargyloxy           >200 (decomp)               218 2-Cl H H      ##STR96##      O  N CH COCH.sub.3 N OCH.sub.3 oil NMR      219 2-Cl H H     ##STR97##      O  N CH COCH.sub.3 N OCH.sub.3 127-128      220 2-Cl H H     ##STR98##      O  N CH COCH.sub.3 N OCH.sub.3 154-155  222 2-OC.sub.3 H.sub.7 H H COOH O     H H N CH COCH.sub.3 N OCH.sub.3 Li.sup.+  salt             >273 (decomp) 2     28 2-Cl 5-Cl H COOH O  N CH COCH.sub.3 N OCH.sub.3 Na.sup.+  salt          >210 (decomp) 235 2-Cl 5-Cl H COOH OH H N CH COCH.sub.3 N OCH.sub.3 N     a.sup.+  salt             >205 (decomp) 239 2-Cl H H COOCH.sub.2 O  N CH C    O     CH.sub.3 N OCH.sub.3 86-87     CHCHCl                242 2-Cl H H      ##STR99##      OCH.sub.3 H N CH COCH.sub.3 N OCH.sub.3 112-113  243 H H H COOH O  N CH C    O     CH.sub.3 N OCH.sub.3 Na.sup.+  salt             >295 (decomp) 244 2-F H     H COOH O  N CH COCH.sub.3 N OCH.sub.3 Li.sup.+  salt             276     (decomp) 247 2-Cl H H COOC.sub.3 H.sub.7 O  N CH COCH.sub.3 N OCH.sub.3     63-65 249 2-Cl 5-Cl H COOCH.sub.3 O  N CH COCH.sub.3 N OCH.sub.3 130-132     251 2-Cl H H COOCH.sub.2 CHCHCl O  N CH COCH.sub.3 N OCH.sub.3 107-108     262 2-Cl 5-Cl H COOallyl O  N CH COCH.sub.3 N OCH.sub.3 89-90 264 2-Cl     5-Cl H COOC.sub.12 H.sub.25 O  N CH COCH.sub.3 N OCH.sub.3 oil NMR 274     2-F 5-F H COOH O  N CH COCH.sub.3 N OCH.sub.3 Na.sup.+  salt     >295 (decomp) 277 2-Cl H H COOC.sub.4 H.sub.9 O  N CH COCH.sub.3 N     OCH.sub.3 NMR 281 2-Cl H H COOC.sub.5 H.sub.11 O  N CH COCH.sub.3 N     OCH.sub.3 NMR 287 2-Cl H H COOC.sub.6 H.sub.13 O  N CH COCH.sub.3 N     OCH.sub.3 70-71 299 2-Cl H H COOC.sub.7 H.sub.15 O  N CH COCH.sub.3 N     OCH.sub.3 NMR 300 2-Cl H H COOC.sub.8 H.sub.17 O  N CH COCH.sub.3 N     OCH.sub.3 NMR 306 5-Cl H H COOH O  N CH COCH.sub.3 N OCH.sub.3 Na.sup.+     salt             266-276 (decomp) 308 2-Cl H H COOC.sub.12 H.sub.25 O  N     CH COCH.sub.3 N OCH.sub.3 NMR      314 2-Cl H H     ##STR100##      O  N CH COCH.sub.3 N OCH.sub.3 92-94  315 2-Cl H H CH.sub.2 OH OH H N     CH COCH.sub.3 N OCH.sub.3 115-116 316 2-Cl H H COOiC.sub.3 H.sub.7 O  N     CH COCH.sub.3 N OCH.sub.3 109-110 321 5-Cl H H COOCH.sub.3 O  N CH     COCH.sub.3 N OCH.sub.3 115-116 423 5-Cl H H COOallyl O  N CH COCH.sub.3     N OCH.sub.3 117-118 425 2-Cl H H CH.sub.2O  OH N CH COCH.sub.3 N     OCH.sub.3 92-94 460  2-OCH.sub.3 5-Cl H COOH O  N CH COCH.sub.3 N     OCH.sub.3 Na.sup.+  salt             228-230 461 2-OCH.sub.3 5-Cl H COOH O       N CH COCH.sub.3 N OCH.sub.3 H.sub.3 N.sup.+ iC.sub.3 H.sub.7 salt            190-201 478 2-OCH.sub.3 5-Cl H COOH OH H N CH COCH.sub.3 N     OCH.sub.3 Li.sup.+  salt             150-160 479 2-Cl 5-Cl H COOH O  N     CH COCH.sub.3 N OCH.sub.3 H.sub.2 N.sup.+ (iC.sub.3 H.sub.7).sub.2 salt                160-162 480 2-Cl 5-Cl H COOH O  N CH COCH.sub.3 N OCH.sub.3     H.sub.2 N.sup.+ (CH.sub.3).sub.2 salt             152-154 481 2-Cl 5-Cl     H COOH O  N CH COCH.sub.3 N OCH.sub.3 H.sub.3 N.sup.+ iC.sub.3 H.sub.7     salt             184-186 489 2-Cl 5-Cl H CON(CH.sub.3).sub.2 O  N CH     COCH.sub.3 N OCH.sub.3 145-147 502 2-Cl H H COOH O  N CH COCH.sub.3 N     OCH.sub.3 NH.sub.4 salt             157-160 503 2-Cl H H COOH O  N CH     COCH.sub.3 N OCH.sub.3 H.sub.3 N.sup.+ iC.sub.3 H.sub.7 salt     136-139 504 2-Cl H H COOH O  N CH COCH.sub.3 N OCH.sub.3 H.sub.2 N.sup.+     (CH.sub.3).sub.2 salt             163-165 527 2-Cl 5-F H CON(CH.sub.3).su     b.2 O  N CH COCH.sub.3 N OCH.sub.3 113-114 528 2-Cl 5-F H COOH O  N CH     COCH.sub.3 N OCH.sub.3 H.sub.3 N.sup.+ iC.sub.3 H.sub.7 salt     174-176 (decomp) 531 2-Cl 5-Cl H COOH O  N CH COCH.sub.3 N OCH.sub.3     H.sub.3 N.sup.+ C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OH.sup.(1) salt         81-83 532 2-Cl H H COOH O  N CH COCH.sub.3 N OCH.sub.3 DGA salt            gum 533 2-Cl 5-CH.sub.3 H COOH O  N CH COCH.sub.3 N OCH.sub.3     H.sub.3 N.sup.+ iC.sub.3 H.sub.7 salt             156-159 534 2-Cl     5-OCH.sub.3 H COOH O  N CH COCH.sub.3 N OCH.sub.3 H.sub.3 N.sup.+     iC.sub.3 H.sub.7 salt             182-184 535 2-CH.sub.3 5-F H COOH O  N     CH COCH.sub.3 N OCH.sub.3 H.sub.3 N.sup.+ iC.sub.3 H.sub.7 salt        161-162 536 2-CH.sub.3 5-Cl H COOH O  N CH COCH.sub.3 N OCH.sub.3     H.sub.3 N.sup.+ iC.sub.3 H.sub.7 salt             164-165 537 2-Cl 4-Cl     H COOH O  N CH COCH.sub.3 N OCH.sub.3 H.sub.3 N.sup.+ iC.sub.3 H.sub.7     salt             150-151 538 2-SCH.sub.3 H H COOH OH H N CH COCH.sub.3 N O     CH.sub.3 Na.sup.+  salt             205-215 (decomp) 539 2-Cl 5-F H COOH     OH H N CH COCH.sub.3 N OCH.sub.3 Na.sup.+  salt             216-225     (decomp) 542 2-Cl 5-CH.sub.3 H CON(CH.sub.3).sub.2 O  N CH COCH.sub.3 N     OCH.sub.3 128-129 544 2-Cl 5-CH.sub.3 H COOCH.sub.3 O  N CH COCH.sub.3 N     OCH.sub.3 87-88      545 2-Cl 5-Cl H     ##STR101##      O  N CH COCH.sub.3 N OCH.sub.3 102-104      547 2-Cl 5-Cl H     ##STR102##      O  N CH COCH.sub.3 N OCH.sub.3 95-97      548 2-Cl 5-OCH.sub.3 H CON(CH.sub.3).sub.2 O  N CH COCH.sub.3 N     OCH.sub.3 130-131 550 2-Cl 5-OCH.sub.3 H COOH O  N CH COCH.sub.3 N     OCH.sub.3 Na.sup.+      salt             225-227 (decomp) 556 2-Cl 5-OCH.sub.3 H COOH OH H N CH C    O     CH.sub.3 N OCH.sub.3 Li.sup.+  salt             182-185 (decomp) 557     2-Cl 5-OCH.sub.3 H COOCH.sub.3 O  N CH COCH.sub.3 N OCH.sub.3 144-145     559 2-CF.sub.3 H H COOH O  N CH COCH.sub.3 N OCH.sub.3 H.sub.3 N.sup.+     iC.sub.3      H.sub.7 salt             124-125 560 2-CF.sub.3 H H CON(CH.sub.3).sub.2 O       N CH COCH.sub.3 N OCH.sub.3 94-95 561 2-CF.sub.3 H H COOH OH H N CH     COCH.sub.3 N OCH.sub.3 Li.sup.+  salt             95-100 (decomp) 563     2-SO.sub.2 CH.sub.3 H H COOH OH H N CH COCH.sub.3 N OCH.sub.3 Na.sup.+     salt             191-198 (decomp) 566 2-CH.sub.3 H H COOH O  N CH     COCH.sub.3 N OCH.sub.3 Li.sup.+ salt             >260 567 2-CH.sub.3 H H C     OOH OH H N CH COCH.sub.3 N OCH.sub.3 Li.sup.+  salt             190-199     570 2-SCH.sub.3 5-Cl H COOH OH H N CH COCH.sub.3 N OCH.sub.3 Li.sup.+     salt             183-185                    577 2-Cl 5-Cl H     ##STR103##      O  N CH COCH.sub.3 N OCH.sub.3 53-56      578 2-Cl 5-Cl H     ##STR104##      O  N CH COCH.sub.3 N OCH.sub.3 134-136      581 2-CH.sub.3 5-F H CON(CH.sub.3).sub.2 O  N CH COCH.sub.3 N OCH.sub.3     125-127 583 2-SCH.sub.3 H H COOH O  N CH COCH.sub.3 N OCH.sub.3 Na.sup.+      salt             286-289 (decomp) 585 2-NH.sub.2 H H COOH O  N CH     COCH.sub.3 N OCH.sub.3 Na.sup.+  salt             265-270 (decomp) 586     2-SO.sub.2 CH.sub.3 H H COOH O  N CH COCH.sub.3 N OCH.sub.3 Na.sup.+     salt             265-266 587 2-SO.sub.2 CH.sub.3 H H COOH O  N CH     COCH.sub.3 N OCH.sub.3 H.sub.3 N.sup.+ iC.sub.3 H.sub.7 salt     84-90 (decomp) 589 2-CH.sub.3 5-F H COOH OH H N CH COCH.sub.3 N OCH.sub.3      Li.sup.+  salt             176-181 (decomp) 592 2-SO.sub.2 CH.sub.3     5-Cl H COOH OH H N CH COCH.sub.3 N OCH.sub.3 Li.sup.+  salt     213-216 (decomp)                   593 2-Cl 5-Cl H     ##STR105##      O  N CH COCH.sub.3 N OCH.sub.3 165- 166      594 2-Cl 5-Cl H     ##STR106##      O  N CH COCH.sub.3 N OCH.sub.3 123-125  596 2-Cl 5-NO.sub.2 H CN CN H N C     H COCH.sub.3 N OCH.sub.3 174.5-175.5 600 2-Cl 5-NO.sub.2 H COOH O  N CH  O     CCH.sub.3 N OCH.sub.3 H.sub.3 N.sup.+ iC.sub.3 H.sub.7 salt     168-170      604 2-Cl 5-Cl H     ##STR107##      O  N CH COCH.sub.3 N OCH.sub.3 143-144      613 2-Br H H CON(CH.sub.3).sub.2 O  N CH COCH.sub.3 N OCH.sub.3 134-135     614 2-Br H H COOH O  N CH COCH.sub.3 N OCH.sub.3 Na.sup.+  salt        285-286 616 2-Br H H COOH OH H N CH COCH.sub.3 N OCH.sub.3 Na.sup.+     salt             166-174 (decomp) 617 2-CN H H COOH O  N CH COCH.sub.3 N O     CH.sub.3 H.sub.3 N.sup.+ iC.sub.3 H.sub.7 salt             160-162 619     2-CN H H COOH O  N CH COCH.sub.3 N OCH.sub.3 Na.sup.+  salt     293-295 (decomp) 620 2-CN H H CON(CH.sub.3).sub.2 O  N CH COCH.sub.3 N     OCH.sub.3 150-151 621 2-CN H H COOH OH H N CH COCH.sub.3 N OCH.sub.3     Na.sub.+  salt             118-125 (decomp) 627 2-Cl 5-Cl H CN CN H N CH     COCH.sub.3 N OCH.sub.3 134-136 628 2-Cl 3-Cl H CN CN H N CH COCH.sub.3 N     OCH.sub.3 122-125     .sup.(1) H.sub.3 N.sup.+ C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OH is also know     as diglycolamine or DGA

                                      TABLE D                                     __________________________________________________________________________     ##STR108##                                                                   Cpd                                                     melting point         No A (anti clockwise)*                                                                        R            X    Y  W.sub.1                                                                          W.sub.2                                                                          W.sub.3                                                                             W.sub.4                                                                          R.sub.1                                                                           (°C.)          __________________________________________________________________________    65 SCHCH                                                                                       ##STR109##       H  N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         125-127               66 SCHCH                                                                                       ##STR110##       H  N  N  COCH.sub.3                                                                          N  OCH.sub.3                                                                         oil NMR               67 CHCHCHN      COOH         OH   CH.sub.3                                                                         N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         Li.sup.+  salt                                                                >283                                                                          (decomp)              119                                                                               ##STR111##  CONHCH.sub.3 OH   H  N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         oil NMR               142                                                                              CHCHCHN      COOC.sub.2 H.sub.5                                                                         CN   H  N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         109-111               149                                                                              CHCHCHN      COOH         OH   H  N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         Li.sup.+  salt                                                                160-165                                                                       (decomp)              150                                                                              CHCHCHN      CONHC.sub.3 H.sub.7                                                                        OH   H  N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         oil NMR               173                                                                              CHCHCHN      COOH         OH   H  N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         142-145                                                                       (decomp)              174                                                                              CHCH CHN     COOCH.sub.3  OH   H  N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         oil NMR               176                                                                              CHCHCHN      COOCH.sub.3  O       N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         129-131               178                                                                               ##STR112##  COOCH.sub.3  H    H  N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         oil NMR               179                                                                               ##STR113##  COOH         H    H  N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         Li.sup.+  salt                                                                >240 (decomp)         186                                                                               ##STR114##  COOCH.sub.3  O       N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         147-149               187                                                                               ##STR115##  COOH         O       N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         Na.sup.+  salt                                                                235                   198                                                                               ##STR116##  COOCH.sub.3  Br   H  N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         125-126               199                                                                              CHCHCHN      COOH         OH   H  N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         Na.sup.+  salt                                                                242 (decomp)          206                                                                               ##STR117##  COOCH.sub.3  acetoxy                                                                            H  N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         oil NMR               216                                                                               ##STR118##  COOC.sub.2 H.sub.5                                                                         H    H  N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         oil NMR               236                                                                               ##STR119##  COOC.sub.2 H.sub.5                                                                         Br   H  N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         oil NMR               237                                                                               ##STR120##  COOC.sub.2 H.sub.5                                                                         Br   H  N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         oil NMR               238                                                                               ##STR121##  COOC.sub.2 H.sub.5                                                                         Br   H  N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         oil NMR               248                                                                               ##STR122##  COOC.sub.2 H.sub.5                                                                         O       N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         103-104               254                                                                               ##STR123##  COOH         O       N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         180-185 (decomp)      301                                                                              CHCHCHN      CON(C.sub.2 H.sub.5).sub.2                                                                 H    H  N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         69-72                 302                                                                              CHCHCHN      COOH         OH   H  N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         K.sup.+  salt                                                                 220-230                                                                       (decomp)              330                                                                              CHCHCHN      CON(C.sub.2 H.sub.5).sub.2                                                                 OtC.sub.4 H.sub.9                                                                  H  N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         oil NMR               414                                                                              NCHCHCH                                                                                     ##STR124##       OH N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         136-138               415                                                                              CHCHCHN                                                                                     ##STR125##  O       CH CH CH    CH CF.sub.3                  416                                                                              CHCHCHN                                                                                     ##STR126##  OH   H  CH CH CH    CH CF.sub.3                  417                                                                              CHCHCHN                                                                                     ##STR127##  OH   H  CH CH CH    CH CF.sub.3                  418                                                                              CHCHCHN                                                                                     ##STR128##  OH   H  CH CH CH    CH CF.sub.3                  419                                                                              NCHCHCH                                                                                     ##STR129##  O       CH CH CH    CH CF.sub.3                  420                                                                              NCHCHCH                                                                                     ##STR130##  OH   H  CH CH CH    CH CF.sub.3                  421                                                                              NCHCHCH                                                                                     ##STR131##  OH   H  CH CH CH    CH CF.sub.3                  422                                                                              NCHCHCH                                                                                     ##STR132##  OH   H  CH CH CH    CH CF.sub.3                  426                                                                              NCHCHCH                                                                                     ##STR133##       OH N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         163-165               511                                                                               ##STR134##  COOCH.sub.3  O(t)C.sub.4 H.sub.9                                                                H  N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         115-117               512                                                                               ##STR135##  CONHC.sub.6 H.sub.13                                                                       OH   H  N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         94-97                 518                                                                               ##STR136##  COOH         O       N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         NMR                   523                                                                               ##STR137##  COOC.sub.2 H.sub.5                                                                         H    H  N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         NMR                   524                                                                               ##STR138##  COOC.sub.2 H.sub.5                                                                         O       N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         98-99                 525                                                                               ##STR139##  COOH         O       N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         Li.sup.+  salt                                                                >280°          529                                                                               ##STR140##  COOC.sub.2 H.sub.5                                                                         H    H  N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         83-85                 540                                                                               ##STR141##  COOC.sub.2 H.sub.5                                                                         O       N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         163-165               541                                                                               ##STR142##  COOH         O       N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         Li.sup.+  salt                                                                275-280               551                                                                               ##STR143##  CON(CH.sub.3).sub.2                                                                        O       N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         138-140               552                                                                               ##STR144##  COOC.sub.2 H.sub.5                                                                         H    H  N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         89-92                 553                                                                               ##STR145##  COOC.sub.2 H.sub.5                                                                         Br   H  N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         NMR                   554                                                                               ##STR146##  COOC.sub.2 H.sub.5                                                                         O       N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         116-118               555                                                                               ##STR147##  COOH         O       N  CH COCH.sub.3                                                                          N  OCH.sub.3                                                                         Li.sup.+  salt                                                                >275                  __________________________________________________________________________     *Left hand atom attached to Rbearing carbon                              

    TABLE E      ##STR148##       Cpd # Y.sub.1 Y.sub.2 Y.sub.3 R X Y W.sub.1 W.sub.2 W.sub.3 W.sub.4     R.sub.1 m.p.       63 H H H COOH O N CH COCH.sub.3 N OCH.sub.3 164-166 64 H H H COOH OH H N      CH COCH.sub.3 N OCH.sub.3 90-92 82 H H H CONH.sub.2 OH H N CH COCH.sub.3      N OCH.sub.3 135-137 83 H H H CONHbenzyl OH H N CH COCH.sub.3 N OCH.sub.3      NMR 84 H H H CONHallyl OH H N CH COCH.sub.3 N OCH.sub.3 NMR 91 H H H     COOCH.sub.3 O N CH COCH.sub.3 N OCH.sub.3 119-121 97 H H H COObenzyl OH     H N CH COCH.sub.3 N OCH.sub.3 NMR 108 H H H CONHCH.sub.3 OH H N CH     COCH.sub.3 N OCH.sub.3 127-129 110 H H H CONHC.sub.3 H.sub.7 OH H N CH     COCH.sub.3 N OCH.sub.3 oil NMR 111 H H H CONHC.sub.6 H.sub.13 OH H N CH  O     CCH.sub.3 N OCH.sub.3 67-69 112 H H H CONH(i)C.sub.3 H.sub.7 OH H N CH     COCH.sub.3 N OCH.sub.3 oil NMR 127 H H H CONHallyl benzoyloxy H N CH     COCH.sub.3 N OCH.sub.3 NMR 128 H H H CONHallyl acetoxy H N CH COCH.sub.3     N OCH.sub.3 NMR 129 H H H CONH.sub.2 ethoxy- H N CH COCH.sub.3 N     OCH.sub.3 112-114      carbonyloxy 130 H H H CONHC.sub.12 H.sub.25 OH H     N CH COCH.sub.3 N OCH.sub.3 oil NMR 131 H H H CONHC.sub.2 H.sub.4     OCH.sub.3 OH H N CH COCH.sub.3 N OCH.sub.3 79-80 132 H H H CONH.sub.2     NH.sub.2 OH H N CH COCH.sub.3 N OCH.sub.3 75-78 133 H H H CONHallyl     OCONHCH.sub.3 H N CH COCH.sub.3 N OCH.sub.3 NMR 144 H H H CONHpropargyl     OH H N CH COCH.sub.3 N OCH.sub.3 102-104      151 H H H     ##STR149##      OH H N CH COCH.sub.3 N OCH.sub.3 oil NMR      152 H H H     ##STR150##      OH H N CH COCH.sub.3 N OCH.sub.3 oil NMR  155 H H H CONHC.sub.18     H.sub.37 OH H N CH COCH.sub.3 N OCH.sub.3 64-66      157 H H H     ##STR151##      OH H N CH COCH.sub.3 N OCH.sub.3 102-104      158 H H H CONH.sub.2 benzoyloxy H N CH COCH.sub.3 N OCH.sub.3 115-116     159 H H H CON(benzoyl).sub.2 benzoyloxy H N CH COCH.sub.3 N OCH.sub.3     168-170      160 H H H     ##STR152##      OH H N CH COCH.sub.3 N OCH.sub.3 88-90      161 H H H CONH.sub.2     ##STR153##      H N CH COCH.sub.3 N OCH.sub.3 138-140      162 H H H     ##STR154##      ##STR155##      H N CH COCH.sub.3 N OCH.sub.3 198-200      164 H H H     ##STR156##      OH H N CH COCH.sub.3 N OCH.sub.3 91-94      168 H H H     ##STR157##      OH H N CH COCH.sub.3 N OCH.sub.3 103-106              169 H H H      ##STR158##      H N CH COCH.sub.3 N OCH.sub.3 135-137  170 H H H CONHNH(t)C.sub.4     H.sub.9 OH H N CH COCH.sub.3 N OCH.sub.3 109-110      171 H H H     ##STR159##      OH H N CH COCH.sub.3 N OCH.sub.3 NMR      172 H H H     ##STR160##      OH H N CH COCH.sub.3 N OCH.sub.3 140-142  177 H H H CONHC.sub.2 H.sub.4     N(CH.sub.3).sub.2 OH H N CH COCH.sub.3 N OCH.sub.3 NMR  182 H H H      ##STR161##      OH H N CH COCH.sub.3 N OCH.sub.3 117-120      183 H H H     ##STR162##      OH H N CH COCH.sub.3 N OCH.sub.3 132-133      184 H H H     ##STR163##      OH H N CH COCH.sub.3 N OCH.sub.3 113-114  185 H H H CONHSO.sub.2     CH.sub.3 OH H N CH COCH.sub.3 N OCH.sub.3 133-135      188 H H H     ##STR164##      OH H N CH COCH.sub.3 N OCH.sub.3 115-117  189 H H H CONHCH.sub.2     COOCH.sub.3 OH H N CH COCH.sub.3 N OCH.sub.3 97-99      193 H H H     ##STR165##      OH H N CH COCH.sub.3 N OCH.sub.3 oil NMR      196 H H H     ##STR166##      OH H N CH COCH.sub.3 N OCH.sub.3 oil NMR  199 H H H COOH OH H N CH     COCH.sub.3 N OCH.sub.3      200 H H H     ##STR167##      OH H N CH COCH.sub.3 N OCH.sub.3 144-146      201 H H H     ##STR168##      OH H N CH COCH.sub.3 N OCH.sub.3 oil NMR      207 H H H CONH.sub.2 dichloro- H N CH COCH.sub.3 N OCH.sub.3 118-119       acetoxy      209 H H H     ##STR169##      OH H N CH COCH.sub.3 N OCH.sub.3 NMR      210 H H H     ##STR170##      OH H N CH COCH.sub.3 N OCH.sub.3 119-121      211 H H H     ##STR171##      OH H N CH COCH.sub.3 N OCH.sub.3 125-127      212 H H H     ##STR172##      OH H N CH COCH.sub.3 N OCH.sub.3 oil NMR      213 H H H     ##STR173##      OH H N CH COCH.sub.3 N OCH.sub.3 oil NMR      214 H H H     ##STR174##      OH H N CH COCH.sub.3 N OCH.sub.3 oil NMR      215 H H H     ##STR175##      OH H N CH COCH.sub.3 N OCH.sub.3 119-120      217 H H H     ##STR176##      OH H N CH COCH.sub.3 N OCH.sub.3 182-183      221 H H H     ##STR177##      OH H N CH COCH.sub.3 N OCH.sub.3 105-106      223 H H H     ##STR178##      OH H N CH COCH.sub.3 N OCH.sub.3 130-131      224 H H H     ##STR179##      OH H N CH COCH.sub.3 N OCH.sub.3 149-150      225 H H H     ##STR180##      OH H N CH COCH.sub.3 N OCH.sub.3 98-100      226 H H H     ##STR181##      OH H N CH COCH.sub.3 N OCH.sub.3 40-42      227 H H H     ##STR182##      OH H N CH COCH.sub.3 N OCH.sub.3 NMR      229 H H H     ##STR183##      OH H N CH COCH.sub.3 N OCH.sub.3 121-123      230 H H H     ##STR184##      OH H N CH COCH.sub.3 N OCH.sub.3 130-132      231 H H H     ##STR185##      OH H N CH COCH.sub.3 N OCH.sub.3 138-140      232 H H H     ##STR186##      OH H N CH COCH.sub.3 N OCH.sub.3 152-154  233 H H H CONHC.sub.3 H.sub.6     N(CH.sub.3).sub.2 OH H N CH COCH.sub.3 N OCH.sub.3 NMR 234 H H H     CONHC.sub.2 H.sub.4 N(C.sub.2 H.sub.5).sub.2 OH H N CH COCH.sub.3 N     OCH.sub.3 NMR 241 H H H COOH OH "H1" N CH COCH.sub.3 N OCH.sub.3     Li.sup.+  salt             158-160      245 H H H     ##STR187##      OH H N CH COCH.sub.3 N OCH.sub.3 150-154      246 H H H     ##STR188##      OH H N CH COCH.sub.3 N OCH.sub.3 133-134      252 H H H     ##STR189##      OH H N CH COCH.sub.3 N OCH.sub.3 150-151      255 H H H     ##STR190##      OH H N CH COCH.sub.3 N OCH.sub.3 52-54      257 H H H     ##STR191##      OH H N CH COCH.sub.3 N OCH.sub.3 NMR  259 H H H CONHC.sub.8 H.sub.17 OH     H N CH COCH.sub.3 N OCH.sub.3 54-56      271 H H H     ##STR192##      OH N CH COCH.sub.3  N OCH.sub.3 137-138      272 H H H COOH O N CH COCH.sub.3 N OCH.sub.3 Li.sup.+  salt     210 (decomp)      273 H H H     ##STR193##      O N CH COCH.sub.3 N OCH.sub.3 147-149                   275 H H H     ##STR194##      OH H N CH COCH.sub.3 N OCH.sub.3 158-160  276 H H H COOH O N CH     COCH.sub.3 N OCH.sub.3 Na.sup.+  salt            195 (decomp)     K.sup.+  salt            (255 decomp) 278 H H H CONHC.sub.9 H.sub.19 OH     H N CH COCH.sub.3 N OCH.sub.3 45-47 279 H H H CONHC.sub.10 H.sub.21 OH H     N CH COCH.sub.3 N OCH.sub.3 49-51      280 H H H     ##STR195##      OH H N CH COCH.sub.3 N OCH.sub.3 58-62  282 H H H CONHCH.sub.2 iPr OH H     N CH COCH.sub.3 N OCH.sub.3 103-105 283 H H H CONHCH.sub.2      CH(OCH.sub.3).sub.2 OH H N CH COCH.sub.3 N OCH.sub.3 NMR 284 H H H     CONHC(CH.sub.3).sub.2CCH OH H N CH COCH.sub.3 N OCH.sub.3 NMR 285 H H H     CONHC.sub.4 H.sub.9 OH H N CH COCH.sub.3 N OCH.sub.3 NMR  286 H H H      ##STR196##      OH H N CH COCH.sub.3 N OCH.sub.3 NMR      288 H H H     ##STR197##      OH H N CH COCH.sub.3 N OCH.sub.3 182-184      289 H H H     ##STR198##      OH H N CH COCH.sub.3 N OCH.sub.3 181-183      290 H H H     ##STR199##      OH H N CH COCH.sub.3 N OCH.sub.3 NMR  291 H H H CONHC.sub.6 H.sub.12     N(CH.sub.3).sub.2 OH H N CH COCH.sub.3 N OCH.sub.3 NMR 292 H H H     CONHC.sub.4 H.sub.8 N(CH.sub.3).sub.2 OH H N CH COCH.sub.3 N OCH.sub.3     NMR      293 H H H     ##STR200##      OH H N CH COCH.sub.3 N OCH.sub.3 131-132      294 H H H     ##STR201##      OH H N CH COCH.sub.3 N OCH.sub.3 124-126      295 H H H     ##STR202##      OH H N CH COCH.sub.3 N OCH.sub.3 NMR      296 H H H     ##STR203##      OH H N CH COCH.sub.3 N OCH.sub.3 88-90      297 H H H     ##STR204##      OH H N CH COCH.sub.3 N OCH.sub.3 NMR      298 H H H     ##STR205##      OH H N CH COCH.sub.3 N OCH.sub.3 NMR      303 H H H     ##STR206##      OH H N CH COCH.sub.3 N OCH.sub.3 NMR      304 H H H     ##STR207##      OH H N CH COCH.sub.3 N OCH.sub.3 54-56      305 H H H     ##STR208##      OH H N CH COCH.sub.3 N OCH.sub.3 D(+) 64-68L(-) NMR      309 H H H     ##STR209##      OH H N CH COCH.sub.3 N OCH.sub.3 133-134      310 H H H     ##STR210##      OH H N CH COCH.sub.3 N OCH.sub.3 102-104      311 H H H     ##STR211##      OH H N CH COCH.sub.3 N OCH.sub.3 122-123      312 H H H     ##STR212##      OH H N CH COCH.sub.3 N OCH.sub.3 126-128      313 H H H     ##STR213##      OH H N CH COCH.sub.3 N OCH.sub.3 106-108  318 H H H COOH OH H N CH     COCH.sub.3 N CH.sub.3 Li.sup.+  salt             185-188 (decomp) 322 H     H H COOH OH H N CH CCH.sub.3 N CH.sub.3 Li.sup.+  salt             >195     (decomp) 323 H H H COOH OH H N CH COCH.sub.3 N H Li.sup.+  salt        >225 (decomp) 324 H H H COOH OH H N CH C OCH.sub.3 N OC.sub.2 H.sub.5     Li.sup.+  salt             195 (decomp) 325 H H H COOH OH H N CH     COCH.sub.3 N Cl      327 H H H     ##STR214##      H H N CH COCH.sub.3 N OCH.sub.3 96-98                  328 H H H     ##STR215##      O N CH COCH.sub.3 N OCH.sub.3 114-116      329 H H H     ##STR216##      O N CH COCH.sub.3 N OCH.sub.3 146-148  379 H H H CON(C.sub.2      H.sub.5).sub.2 O N CH COCH.sub.3 N OCH.sub.3 109-111 380 H H H CON(C.sub     .2      H.sub.5).sub.2 OH H N CH COCH.sub.3 N OCH.sub.3 381 H H H CON(iC.sub.3     H.sub.7).sub.2 O N CH COCH.sub.3 N OCH.sub.3 146-148 382 H H H CON(iC.sub     .3 H.sub.7).sub.2 OH H N CH COCH.sub.3 N OCH.sub.3              383 H H     H      ##STR217##      O N CH COCH.sub.3 N OCH.sub.3                   384 H H H     ##STR218##      OH H N CH COCH.sub.3 N OCH.sub.3  385 H H H CON(CH.sub.3).sub.2 O N CH  O     CCH.sub.3 N OCH.sub.3  121-123 386 H H H CON(CH.sub.3).sub.2 OH H N CH     COCH.sub.3 N OCH.sub.3                  387 H H H     ##STR219##      O N CH COCH.sub.3 N OCH.sub.3                   388 H H H     ##STR220##      OH H N CH COCH.sub.3 N OCH.sub.3                  389 H H H     ##STR221##      O N CH COCH.sub.3 N OCH.sub.3 131-133                   390 H H H     ##STR222##      OH H N CH COCH.sub.3 N OCH.sub.3                  391 H H H     ##STR223##      O N CH COCH.sub.3 N OCH.sub.3                   392 H H H     ##STR224##      OH H N CH COCH.sub.3 N OCH.sub.3                  393 H H H     ##STR225##      O N CH COCH.sub.3 N OCH.sub.3 NMR                    394 H H H     ##STR226##      OH H N CH COCH.sub.3 N OCH.sub.3                  395 H H H     ##STR227##      O N CH COCH.sub.3 N OCH.sub.3 oil NMR                   396 H H H     ##STR228##      OH H N CH COCH.sub.3 N OCH.sub.3                  397 H H H     ##STR229##       O N CH COCH.sub.3 N OCH.sub.3                   398 H H H     ##STR230##      OH H N CH COCH.sub.3 N OCH.sub.3                  399 H H H     ##STR231##      O N CH COCH.sub.3 N OCH.sub.3                   400 H H H     ##STR232##      OH H N CH COCH.sub.3 N OCH.sub.3                   401 H H H     ##STR233##      O N CH COCH.sub.3 N OCH.sub.3                   402 H H H     ##STR234##      OH H N CH COCH.sub.3 N OCH.sub.3                  403 H H H     ##STR235##      O N CH COCH.sub.3 N OCH.sub.3 131-133                   404 H H H     ##STR236##      OH H N CH COCH.sub.3 N OCH.sub.3                  405 H H H     ##STR237##      O N CH COCH.sub.3 N OCH.sub.3 143-145                   406 H H H     ##STR238##      OH H N CH COCH.sub.3 N OCH.sub.3      407 H H H     ##STR239##      OH H N CH COCH.sub.3 N OCH.sub.3 gum NMR  411 H H H CONHC.sub.2 H.sub.4     S(n)C.sub.4 H.sub.9 OH H N CH COCH.sub.3 N OCH.sub.3 gum NMR      413 H H H      ##STR240##      O N CH COCH.sub.3 N OCH.sub.3 gum NMR  428 H H H CONHSC.sub.4 H.sub.9     OH H N CH COCH.sub.3 N OCH.sub.3 NMR (racemate) 432 H H H CONHnC.sub.5     H.sub.11 OH H N CH COCH.sub.3 N OCH.sub.3 NMR 433 H H H CONHC.sub.7     H.sub.15 OH H N CH COCH.sub.3 N OCH.sub.3 NMR      434 H H H     ##STR241##      OH H N CH COCH.sub.3 N OCH.sub.3 143-145      435 H H H     ##STR242##      OH H N CH COCH.sub.3 N OCH.sub.3 NMR  436 H H H CONH(s)C.sub.4 H.sub.9     OH H N CH COCH.sub.3 N OCH.sub.3 NMR (both S(+) and             R-(-)     forms) 437 H H H CONHCH.sub.2 C CH OH H N CH CCH.sub.3 N OCH.sub.3 NMR                438 H H H      ##STR243##      OH N CH COCH.sub.3 N OCH.sub.3 139-141                   439 H H H     ##STR244##      OH H N CH COCH.sub.3 N OCH.sub.3 143-144      440 H H H     ##STR245##      OH H N CH COCH.sub.3 N OCH.sub.3 133-134              441 H H H      ##STR246##      O N CH COCH.sub.3 N OCH.sub. 3 117-120                   442 H H H     ##STR247##      OH H N CH COCH.sub.3 N OCH.sub.3 127-128      443 H H H     ##STR248##      OH H N CH COCH.sub.3 N OCH.sub.3 138-140      444 H H H     ##STR249##      OH H N CH COCH.sub.3 N OCH.sub.3 152-153      445 H H H     ##STR250##      OH H N CH COCH.sub.3 N OCH.sub.3 108-110      446 H H H     ##STR251##      OH H N CH COCH.sub.3 N OCH.sub.3 NMR      447 H H H     ##STR252##      OH H N CH COCH.sub.3 N OCH.sub.3 130-131      449 H H H     ##STR253##      OH H N CH COCH.sub.3 N OCH.sub.3 116-117      450 H H H     ##STR254##      OH H N CH COCH.sub.3 N OCH.sub.3 NMR      453 H H H     ##STR255##      OH H N CH COCH.sub.3 N OCH.sub.3 100-102  454 H H H COOH O N CH     COCH.sub.3 N OCH.sub.3 H.sub.3 N.sup.+ iC.sub.3 H.sub.7 salt     201-203 455 H H H COOH O N CH COCH.sub.3 N OCH.sub.3 H.sub.2 N.sup.+     (CH.sub.3).sub.2 salt            183-185      456 H H H     ##STR256##      O N CH COCH.sub.3 N OCH.sub.3 115-116  457 H H H COOH O N CH COCH.sub.3     N OCH.sub.3 H.sub.2 N.sup.+ (iC.sub.3 H.sub.7).sub.2 salt     185-187      458 H H H     ##STR257##      O N CH COCH.sub.3 N OCH.sub.3 NMR                   462 H H H     ##STR258##      OH H N CH COCH.sub.3 N OCH.sub.3 NMR      463 H H H     ##STR259##      OH H N CH COCH.sub.3 N OCH.sub.3 NMR  464 H H H COOH O N CH COCH.sub.3     N OCH.sub.3 diCa.sup.+ +  salt            >240 465 H H H COOH O N CH     COCH.sub.3 N OCH.sub.3 diMg.sup.++  salt            >240 466 H H H COOH     O N CH COCH.sub.3 N OCH.sub.3 diAl.sup.++ OH salt            >250  467 H     H H      ##STR260##      O N CH COCH.sub.3 N OCH.sub.3 148-150                   468 H H H     ##STR261##      OH H N CH COCH.sub.3 N OCH.sub.3 125-126      469 H H H     ##STR262##      OH H N CH COCH.sub.3 N OCH.sub.3 NMR       470 H H H     ##STR263##      OH H N CH COCH.sub.3 N OCH.sub.3 NMR      471 H H H     ##STR264##      OH H N CH COCH.sub.3 N OCH.sub.3 NMR      472 H H H     ##STR265##      OH H N CH COCH.sub.3 N OCH.sub.3 137-138      473 H H H     ##STR266##      OH H N CH COCH.sub.3 N OCH.sub.3 NMR      474 H H H     ##STR267##      OH H N CH COCH.sub.3 N OCH.sub.3 156-159      475 H H H     ##STR268##      OH H N CH COCH.sub.3 N OCH.sub.3 NMR      482 H H H COOH OH H N CH COCH.sub.3 N OCH.sub.3      ##STR269##       483 H H H COOH OH H N CH COCH.sub.3 N OCH.sub.3 H.sub.3 N.sup.+     C.sub.6 H.sub.13 salt             NMR      484 H H H     ##STR270##      OH H N CH COCH.sub.3 N OCH.sub.3 113-115      485 H H H     ##STR271##      OH H N CH COCH.sub.3 N OCH.sub.3 147-148              487 H H H COOH O     N CH COCH.sub.3 N OCH.sub.3 H.sub.3 N.sup.+ C.sub.6 H.sub.13 salt         165-167      488 H H H COOH O N CH COCH.sub.3 N OCH.sub.3     ##STR272##                   490 H H H     ##STR273##      OH H N CH COCH.sub.3 N OCH.sub.3 NMR      491 H H H     ##STR274##      OH H N CH COCH.sub.3 N OCH.sub.3 NMR  492 H H H COOH O N OH COCH.sub.3     N OCH.sub.3 Al.sup.+ (OH).sub.2 salt            >250 493 H H H COOH O N     OH COCH.sub.3 N OCH.sub.3 Al.sup.++ OH/Phe.sup.-  salt            >250     494 H H H      ##STR275##      O N CH COCH.sub.3 N OCH.sub.3 59-61                   495 H H H     ##STR276##      OH H N CH COCH.sub.3 N OCH.sub.3 148-150              496 H H H      ##STR277##      O N CH COCH.sub.3 N OCH.sub.3 NMR      497 H H H     ##STR278##      O N CH COCH.sub.3 N OCH.sub.3 NMR                   498 H H H     ##STR279##      OH H N CH COCH.sub.3 N OCH.sub.3 NMR                  500 H H H     ##STR280##      O N CH COCH.sub.3 N OCH.sub.3 NMR      501 H H H     ##STR281##      O N CH COCH.sub.3 N OCH.sub.3 NMR  505 H H H CONHCH.sub.2 CH.sub.2 OH     OH H N CH COCH.sub.3 N OCH.sub.3 NMR      506 H H H     ##STR282##      OH H N CH COCH.sub.3 N OCH.sub.3 NMR  507 H H H CON(C.sub.3      H.sub.7).sub.2 O N CH COCH.sub.3 N OCH.sub.3 106-108   508 H H H      ##STR283##      O N CH COCH.sub.3 N OCH.sub.3 NMR      509 H H H     ##STR284##      O N CH COCH.sub.3 N OCH.sub.3 NMR                   510 H H H     ##STR285##      OH H N CH COCH.sub.3 N OCH.sub.3 NMR      513 H H H     ##STR286##      OH H N CH COCH.sub.3 N OCH.sub.3 115-117      514 H H H     ##STR287##      OH H N CH COCH.sub.3 N OCH.sub.3 94-97      515 H H H     ##STR288##      OH H N CH COCH.sub.3 N OCH.sub.3 NMR      516 H H H     ##STR289##      OH H N CH COCH.sub.3 N OCH.sub.3 NMR      517 H H H     ##STR290##      OH H N CH COCH.sub.3 N OCH.sub.3 NMR      519 H H H     ##STR291##      OH H N CH COCH.sub.3 N OCH.sub.3 NMR      520 H H H     ##STR292##      OH H N CH COCH.sub.3 N OCH.sub.3 94-96                  521 H H H     ##STR293##      O N CH COCH.sub.3 N OCH.sub.3 78-79      522 H H H     ##STR294##      O N CH COCH.sub.3 N OCH.sub.3 94-96      427 H H H     ##STR295##      O N CH COCH.sub.3 N OCH.sub.3 131-133      499 H H H     ##STR296##      O N CH COCH.sub.3 N OCH.sub.3 116-118  546 H H H CONHC.sub.2 H.sub.5 OH H      N CH COCH.sub.3 N OCH.sub.3 48-50      558 H H H     ##STR297##      OH H N CH COCH.sub.3 N OCH.sub.3 108-110  562 H H 4-CH.sub.3 COOH OH H     N CH COCH.sub.3 N OCH.sub.3 Li.sup.+  salt             nmr     569 H H H      ##STR298##      O N CH COCH.sub.3 N OCH.sub.3 136-138      571 H H H     ##STR299##      O N CH COCH.sub.3 N OCH.sub.3 NMR  573 H H 4-OCH.sub.3 COOH O N CH     COCH.sub.3 N OCH.sub.3 202-204 574 H H 4-OCH.sub.3 COOH O N CH COCH.sub.3      N OCH.sub.3 Li.sup.+  salt            200-210      575 H H H     ##STR300##      O N CH COCH.sub.3 N OCH.sub.3 122-124      576 H H H     ##STR301##      O N CH COCH.sub.3 N OCH.sub.3 128-131      579 H H H     ##STR302##      O N CH COCH.sub.3 N OCH.sub.3 118-121      584 H H H     ##STR303##      O N CH COCH.sub.3 N OCH.sub.3 168-171      598 H H H     ##STR304##      O N CH COCH.sub.3 N OCH.sub.3 150-152      602 H H H     ##STR305##      O N CH COCH.sub.3 N OCH.sub.3 152-154      603 H H H     ##STR306##      O N CH COCH.sub.3 N OCH.sub.3 90-93      609 H H H     ##STR307##      O N CH COCH.sub.3 N OCH.sub.3 167-170  622 H H H COOsC.sub.4 H.sub.9 O     N CH COCH.sub.3 N OCH.sub.3 NMR 625 H H H COOnC.sub.4 H.sub.9 O N CH     COCH.sub.3 N OCH.sub.3 NMR 626 H H H COOiC.sub.4      H.sub.9 O N CH COCH.sub.3 N OCH.sub.3 111-113      632 H H H     ##STR308##      OH N CH COCH.sub.3 N OCH.sub.3 122-127      633 H H H     ##STR309##      OH N CH COCH.sub.3 N OCH.sub.3 142-144      634 H H H     ##STR310##      OH N CH COCH.sub.3 N OCH.sub.3 156-158     (64: Lithium salt m.p. >250°; sodium salt m.p. >190°     (decomp); potassium salt m.p. >230° (decomp))     Phe = Phenalanine anion

                                      TABLE F                                     __________________________________________________________________________     ##STR311##                                                                   Cpd #                                                                              AA                   X   Y     m.p.                                      __________________________________________________________________________     90                                                                                 ##STR312##          H   H     123-125                                   331                                                                                 ##STR313##          O                                                   332  "                    OH  H                                               333                                                                                 ##STR314##          O                                                   334  "                    OH  H                                               335                                                                                 ##STR315##          O                                                   336  "                    OH  H                                               337                                                                                 ##STR316##          O                                                   338  "                    OH  H                                               339                                                                                 ##STR317##          O                                                   340  "                    OH  H                                               341                                                                                 ##STR318##          O                                                   342  "                    OH  H                                               343                                                                                 ##STR319##          O                                                   344  "                    OH  H                                               345                                                                                 ##STR320##          O                                                   346  "                    OH  H                                               347                                                                                 ##STR321##          O                                                   348  "                    OH  H                                               349                                                                                 ##STR322##          O                                                   350  "                    OH  H                                               351                                                                                 ##STR323##          O                                                   352  "                    OH  H                                               353                                                                                 ##STR324##          O                                                   354  "                    OH  H                                               355                                                                                 ##STR325##          O                                                   356  "                    OH  H                                               357                                                                                 ##STR326##          O                                                   358  "                    OH  H                                               359                                                                                 ##STR327##          O                                                   360  "                    OH  H                                               361                                                                                 ##STR328##          O                                                   362  "                    OH  H                                               363                                                                                 ##STR329##          O                                                   364  "                    OH  H                                               365                                                                                 ##STR330##          O                                                   366  "                    OH  H                                               367                                                                                 ##STR331##          O                                                   368  "                    OH  H                                               369                                                                                 ##STR332##          O                                                   370  "                    OH  H                                               371                                                                                 ##STR333##          O                                                   372  "                    OH  H                                               373                                                                                 ##STR334##          O                                                   374  "                    OH  H                                               375                                                                                 ##STR335##          O                                                   376  "                    OH  H                                               377                                                                                 ##STR336##          O                                                   378  "                    OH  H                                               410                                                                                 ##STR337##          H   H     122-123                                   412  "                    H   O(t)C.sub.4 H.sub.9                                                                 gum NMR                                   424  "                    OH  H     130-131                                   429  "                    O         NMR                                       430                                                                                 ##STR338##          H   O(t)C.sub.4 H.sub.9                                                                 NMR                                       431  "                    OH  H     NMR                                       448                                                                                 ##STR339##          OH  H     NMR                                       451                                                                                 ##STR340##          OH  H     143-144                                   511                                                                                 ##STR341##          H   H     NMR                                       512  "                    H   O(t)C.sub.4 H.sub.9                                                                 NMR                                       513                                                                                 ##STR342##          H   H     92-93                                     514  "                    O         140-142                                   515                                                                                 ##STR343##          H   H     177-179                                   530                                                                                 ##STR344##          H   H     NMR                                       564                                                                                 ##STR345##          O         decompose 270                             565                                                                                 ##STR346##          /   CN    155-158                                   601                                                                                 ##STR347##              OH    124-126                                   635                                                                                 ##STR348##          H   H     92-94                                     __________________________________________________________________________

Compounds of Table F wherein COOH is replaced by other meanings of R aslisted in Tables C, D and E above for R may be prepared analogously.

    __________________________________________________________________________    NMR data [.sup.1 H nmr (CDCl.sub.3)]                                          Cpd No                                                                        __________________________________________________________________________    41   δ: 3.95(s, 6H, OCH.sub.3), 5.95(s, 1H, pyrimidine H), 6.45(s,           1H, OCH), 7.7-9.1(m, 3H, pyridine H).                                    44   δ: 1.32(t, 3H, CH.sub.3), 2.87(q, 2H, CH.sub.2), 4.05(s, 6H,            OCH.sub.3), 6.3(s, 1H, OCH), 7.82(d,                                          1H., arom.), 8.72(d, 1H, arom.).                                         46   δ: 1,32(t, 3H, CH.sub.3), 2.85(q, 2H, CH.sub.2), 3.87(s, 6H,            OCH.sub.3), 5.97(s, 1H, pyrimidine H),                                        6.32(s, 1H, OCH), 8.08(d, 1H, pyridine H), 8.71(d, 1H, pyridine H).      48   δ: 1.25(s, 6H, CH.sub.3), 3.85(s, 6H, OCH.sub.3), 3.95(2H,              OCH.sub.2), 4.65(s, 2H, CH.sub.2),                                            5.85(s, 1H, pyrimidine H), 7.2-8.0(4H, aromatic).                        49   δ: 1.00(s, 6H, CH.sub.3), 3.65 and 3.75(d of d, 2H,                     OCH.sub.2), 6.05(s, 1H, pyrimidine H),                                        7.2-8.1(4H, aromatic H).                                                 54   δ: 2.9(s, 3H, CH.sub.3 N), 3.10(s, 3H, CH.sub.3 O), 3.90(s,             6H, OCH.sub.3), 6.10(s, H, pyrimidine H),                                     7.2-7.9(3H, aromatic H).                                                 61   δ: 1.24(s, 6H, CH.sub.3), 3.98(a, 2H, CH.sub.2 O), 4.74(a, 2H,          CH.sub.2), 7.16(s, 1H, pyrimidine H).                                    65   δ: 3.96(s, 6H, OCH.sub.3), 5.96(9, 1H, pyrimidine H), 6.32(s,           1H, OCR), 7.27(d, 1H, thienyl H),                                             7.85(d, 1H, thienyl H).                                                  66   δ: 4.08(s, 6H, OCH.sub.3), 6.27(s, 1H, OCH), 7.18(d, 1H,                thienyl H), 7.95 (d, 1H, thienyl H).                                     76   δ: 1.63(t, 3H, CH.sub.3), 3.91(s, 6H, OCH.sub.3), 4.1(q, 2H,            OCH.sub.2), 6.08(s, 1H, pyrimidine H),                                        7.2-7.8(m, 3H, aromatic H).                                              83   δ: 3.85(s, 6H, OCH.sub.3), 4.58(d, 2H, NCH.sub.2), 5.30(s, 1H,          OH), 5.80(s, 1H, pyrimidine),                                                 6.82(s, 1H, OCH), 7.25(s, 5H, aromatic), 7.40(dd, 1H, pyridine),              7.98(dd, 1H, pyridine), 8.45(dd, 1H, pyridine),                               8.70(s, 1H, NH).                                                         84   δ: 3.85(s, 6H, OCH.sub.3), 4.05(t, 2H, NCH.sub.2), 5.0-5.45(m,          3H, CH═CH.sub.2), 5.85(s, 1H,                                             pyrimidine), 6.80(s, 1H, OCH), 7.2-8.6(m, 3H, pyridine).                 86   δ: 3.85(s, OCH.sub.3), 5.37(s, OCH.sub.2 Ar), 5.85(s,                   pyrimidine), 6.80(d, OCH), 7.2-8.2(m, aromatic),                              mixture with cpd. 40.                                                    88   δ: 4.00(s, 3H, OCH.sub.3), 5.50(s, 2H, OCH.sub.2), 6.05(s, 1H,          pyrimidine H), 6.27(s, 1H, OCH)                                               7.1-7.7(m, 8H, aromatic H).                                              95   δ: 3.85(s, 6H, OCH.sub.3), 5.42(s, 2H, OCH.sub.2), 6.05(s, 1H,          pyrimidine), 6.42(s, 1H, OCH),                                                7.25(s, 5H, aromatic), 7.30(dd, 1H, pyridine), 7.98(dd, 1H,                   pyridine), 8.90(dd, 1H, pyridine).                                       97   δ: 3.80(s, 6H, OCH.sub.3), 5.35(s, 2H, OCH.sub.2 Ar), 5.85(s,           1H, pyrimidine), 6.65(s, 1H, OCH),                                            7.15-8.6(m, 8H, aromatic), mixture with cpd. 40.                         107  δ: 1.92(s, 3H, C.tbd.CCH.sub.3), 3.98(s, 6H, OCH.sub.3),                4.92(s, 2H, OCH.sub.2), 6.07(s, 1H, pyrimidine),                              6.58(s, 1H, OCH), 7.71(dd, 1H, pyridine), 8.20(dd, 1H, pyridine),             8.90(dd, 1H, pyridine).                                                  110  δ: 0.91(t, 3H, CH.sub.3), 1.53(m, 2H, CH.sub.2) 3.37(m, 2H,             CH.sub.2), 3.81(s, 6H, OCH.sub.3),                                            4.50(m, 3H, OH and NCH.sub.2), 5.82(s, 1H, pyrimidine), 6.72(s, 1H,           OCH), 7.37(dd, 1H, pyridine),                                                 7.95(dd, 1H, pyridine), 8.45(dd, 1H, pyridine).                          112  δ: 1.22(d, 6H, CH.sub.3), 3.81(s, 6H, OCH.sub.3), 4.20(s, 1H,           NCH), 5.85(s, 1H, pyrimidine), 6.71(s, 1H, OCH),                              7.38(dd, 1H, pyridine), 7.92(dd, 1H, pyridine), 8.25(s, 1H, NH),              8.47(dd, 1H, pyridine).                                                  119  δ: 3.05(d, 3H, NCH.sub.3), 3.94(s, 6H, OCH.sub.3), 5.20(s, 1H,          OH), 5.75(s, 1H, pyrimidine),                                                 5.98(s, 1H, OCH), 7.26(d, 1H, pyridine H), 7.82(q, 1H, NH), 8.28(d,           1H, pyridine H).                                                         127  δ: 3.75(s, 6H, OCH.sub.3), 4.05(t, 2H, NCH.sub.2), 5.05-5.5(m,          3H, CH═CH.sub.2),                                                         5.85(s, 1H, pyrimidine), 7.2-8.6(m, 9H, phenyl + OCH).                   128  δ: 2.20(s, 3H, CH.sub.3), 3.75(s, 6H, OCH.sub.3), 4.10(t, 2H,           NCH.sub.2), 5.0-6.6(m, 3H,                                                    CH═CH.sub.2), 5.85(s, 1H, pyrimidine), 7.2-8.6(m, 5H, pyridine +          NH, OCH).                                                                130  δ: 1.30(m, 15H, aliphatic), 2.26(s, 8H, aliphatic), 3.36(m,             2H, NCH.sub.2), 3.83(9, 6H,                                                   OCH.sub.3), 5.82(s, 1H, pyrimidine), 6.81(s, 1H, OCH), 7.38(dd, 1H,           pyridine), 8.06(dd, 1H,                                                       pyridine), 8.29(s, 8.46(dd, 1H, pyridine).                               133  δ: 2.85(d, 3H, NCH.sub.3), 3.85(s, 6H, OCH.sub.3), 4.10(t, 2H,          NCH.sub.2), 5.0-6.0(m, 3H,                                                    CH═CH.sub.2), 5.85(s, 1H, pyrimidine), 7.2-8.6(s, 4H, pyridine +          OCH).                                                                    150  δ: 0.96(t, 3H, CH.sub.3), 1.68(s, 2H, CH.sub.2), 3.50(m, 2H,            NCH.sub.2), 3.93(s, 6H, OCH.sub.3),                                           5.92(s, 1H, pyrimidine H), 6.17(d, 1H, OCH), 7.21(d of d, 1H,                 pyridine H), 8.07(dd, 1H,                                                     pyridine H), 8.57(dd, 1H, pyridine H), 8.66(t, 1H, NH).                  151  δ: 1.50(d, 3H, CH.sub.3), 3.82(s, 6H, OCH.sub.3), 5.21(s, 2H,           NCH, OH), 5.81(s, 1H, pyrimidine),                                            6.85(s, 1H, OCH), 7.23(m, 6H, phenyl and pyridine), 7.89(dd, 1H,              pyridine), 8.42(dd, 1H, pyridine) 8.62(s, 1H, NH).                       152  δ: 2.18(s, 3H, CH.sub.3), 3.89(s, 6H, OCH.sub.3), 4.42(d, 2H,           NCH.sub.2), 5.81(s, 1H, pyrimidine), 6.85(s, 1H,                              OCH), 7.03(s, 4H, phenyl), 7.21(dd, 1H, pyridine), 7.91(dd, 1H,               pyridine), 8.42(dd, 1H, pyridine), 8.51(s, 1H, NH).                      171  δ: 1.24(t, 3H, CH.sub.3), 2.60(q, 2H, CH.sub.2), 3.86(s, 6H,            OCH.sub.3), 4.62(d, 2H, NCH.sub.2),                                           5.86(s, 1H, pyrimidine H), 6.90(d, 1H, OCH), 7.0-8.54(m, 7H,                  phenyl), 8.60(bs, 1H, NH).                                               174  δ: 3.83(s, 3H, OCH.sub.3), 3.90(s, 6H, OCH.sub.3), 5.83(s, 1H,          pyrimidine H), 6.60(d, 1H, OCH),                                              7.30(dd, 1H, pyridine H), 8.23(dd, 1H, pyridine H), 8.70(dd, 1H,              pyridine H).                                                             177  δ: 2.20(s, 6H, CH.sub.3), 2.38(t, 2H, CH.sub.2 N), 3.42(q, 2H,          NCH.sub.2), 3.78(s, 6H, OCH.sub.3),                                           4.88(br, 1H, NH) 5.75(s, 1H, pyrimidine), 6.61(s, 1H, OCH), 7.29(dd,          1H, pyridine), 7.80(dd, 1H, pyridine),                                        8.34(dd, 1H, pyridine).                                                  178  δ: 3.85(s, 9H, OCH.sub.3), 3.95(s, 3H, OCH.sub.3), 4.14(s, 2H,          CH.sub.2), 5.82(s, 1H, pyrimidine H),                                         6.90(d, 1H, pyridine H), 8.12(d, 1H, pyridine H).                        187  δ: 3.70(s, 9H, OCH.sub.3), 5.82(s, 1H, pyrimidine H), ;6.80(d,          1H, pyridine H), 8.10(d, 1H, pyridine H).                                193  δ: 1.00(d, 6H, CH.sub.3), 3.78(s, 3H, OCH.sub.3), 3.85(s, 6H,           OCH.sub.3), 4.72(q, 1H, CH), 5.50(d, 2H,                                      OH and NCH), 5.82(s, 1H, pyrimidine), 6.88(s, 1H, OCH), 7.40(dd, 1H,          pyridine), 7.98(dd, 1H, pyridine), 8.52(dd,                                   1H, pyridine), 8.78(s, 1H, NH).                                          196  δ: 3.78(s, 6H, OCH.sub.3), 4.70(d, 2H, NCH.sub.2), 5.35(s, 1H,          OH), 5.81(s, 1H, pyrimidine), 6.28(m, 2H,                                     furfuryl), 6.81(s, 1H, OCH), 7.30(m, 2H, furfuryl; pyridine),                 7.98(dd, 1H, pyridine), 8.41(dd, 1H, pyridine),                               8.67(s, 1H, NH).                                                         201  δ: 1.87-2.04(m, 4H, CH.sub.2 and tetrahydrofuran),                      3.71-3.92(m, 9H, OCH.sub.3 and tetrahydrofuran),                              5.86-5.87(s, 2H, pyrimidine and OH), 6.74(d, 1H, OCH), 7.39(dd, 1H,           pyridine), 7.88(dd, 1H, pyridine),                                            8.48(dd, 1H, pyridine), 8.55(s, 1H, NH).                                 206  δ: 2.22(s, 1H, CH.sub.3), 3.85(9, 6H, OCH.sub.3), 3.92(s, 3H,           OCH.sub.3), 3.97(s, 3H, OCH.sub.3), 5.86(s,                                   1H, pyrimidine H), 6.80(s, 1H, OCH), 7.10(d, 1H, pyridine H),                 8.16(d, 1H, pyridine H).                                                 209  δ: 3.63(t, 3H, OCH.sub.3), 3.74(s, 6H, OCH.sub.3),                      5.48-5.81(m, 4H, pyrimidine, OH, COCH), 6.88-7.42(m,                          8H, phenyl, OCH, pyridine), 7.95(dd, 1H, pyridine), 8.46(dd, 1H,              pyridine) 9.25(d, 1H, NH).                                               212  δ: 3.85(s, 6H, OCH.sub.3), 4.41-4.52(m, 2H, NCH.sub.2),                 5.21-5.72(d, s, 4H, NH.sub.2, pyrimidine, OH),                                6.61(s, 1H, OCH), 7.12-7.32(m, 3H, pyridine, benzylsulfon),                   7.71-7.80(m, 3H, pyridine, benzylsulfon), 8.3(d, 1H,                          pyridine), 8.71(m, 1H, NH).                                              213  δ: 3.61(s, 6H, OCH.sub.3), 4.60(d, 2H, CH.sub.2, OH), 4.90(s,           1H, OH) 5.72(s, 1H, pyrimidine), 6.72(s,                                      1H, OCH), 7.16-8.41(m, 7H, pyridine), 9.12(s, 1H, NH).                   214  δ: 3.75(s, 6H, OCH.sub.3), 4.73(d, 2H, NCH.sub.2), 5.84(s, 1H,          pyrimidine), 6.86-9.96(m, 3H, OCH,                                            thiophone), 7.15(d, 1H, thiophene), 7.34(dd, Jcb=4.7, Jcd=7.9, 1H,            pyridine), 7.96(dd, Jdc=7.9,                                                  Jdb=1.5, 1H, pyridine) 8.4(dd, Jbc=4.7, Jbd=1.5, 1H, pyridine),               8.71(d, 1H, NH).                                                         216  δ: 1.31(t, 3H, CH.sub.3), 2.62(s, 3H, CH.sub.3), 3.87(s, 6H,            OCH.sub.3), 4.21(s, 2H, CH.sub.2), 4.40(q, 2H,                                OCH.sub. 2), 5.83(s, 1H, pyrimidine H), 7.13(d, 1H, pyridine H),              8.44(d, 1H, pyridine H).                                                 218  δ: 284(3.08)(s, 3H, NCH.sub.3), 3.92(s, 6H, OCH.sub.3),                 4.50-5.03(m, 2H, NCH.sub.2), 6.10(s, 1H, pyrimidine H),                       7.10-7.80(m, 7H, aromatic H).                                            227  δ: 1.50(s, 6H, CH.sub.2), 2.40(a. 6H, NCH.sub.2), 3.55(q, 2H,           NCH.sub.2), 3.80(s, 6H, OCH.sub.3), 5.85(s, 1H,                               pyrimidine H), 6.70(s, 1H, OCH), 7.15-8.60(m, 4H, 3 pyridine H +              NH).                                                                     233  δ: 1.80(q, 2H, CH.sub.2), 2.25(s, 6H, NCH.sub.3), 2.35(q, 2H,           NCH.sub.2), 3.45(q, 2H, NCH.sub.2), 3.80(s, 6H,                               CH.sub.3), 5.80(s, 1H, pyrimidine), 6.65(s, 1H, OCH), 7.15-850(m,             3H, pyridine).                                                           234  δ: 1.00(t, 6H, CH.sub.3), 2.60(m, 6H, NCH.sub.2), 3.50(q, 2H,           NCH.sub.2), 3.92(s, 6H, OCH.sub.3), 5.80(s, 1H,                               pyrimidine H), 6.80(s, 1H, OCH), 7.15-8.7(m, 3H, pyridine).              236  δ: 1.37(t, 3H, CH.sub.3), 2.56(s, 3H, CH.sub.3), 3.87(s, 6H,            OCH.sub.3), 4.43(q, 2H, OCH.sub.2), 5.87(s, 1H,                               pyrimidine H), 6.12(s, 1H, CHBr), 7.90(d, 1H, pyridine H), 8.56(d,            1H, pyridine H).                                                         237  δ: 1.40(t, 3H, CH.sub.3), 3.87(s, 6H, OCH.sub.3), 4.43(q, 2H,           OCH.sub.2), 4.70(s, 2H, CH.sub.2 Br), 5.88(s, 1H,                             pyrimidine H), 6.23(s, 1H, CHBr), 8.07(d, 1H, pyridine H), 8.65(d,            1H, pyridine H).                                                         238  δ: 1.37(t, 3H, CH.sub.3), 2.06(s, 3H, CH.sub.3), 3.88(s, 6H,            OCH.sub.3), 4.40(q, 2H, OCH.sub.2), 5.28(s, 2H,                               OCH.sub.2), 5.87(s, 1H, pyrimidine H), 6.23(s, 1H, CHBr), 8.04(d,             1H, pyridine H), 8.64(d, 1H, pyridine H).                                257  δ: 3.82(s, 6H, OCH.sub.3), 4.06(s, 2H, NCH.sub.2), 5.08(s, 1H,          OH), 5.43(s, 1H, NH), 5.87(s, 1H, OCH), 6.62(s,                               1H, pyrimidine), 7.32-7.38(m, 6H, pyridine; phenyl), 7.88(dd, 1H,             pyridine), 8.45(dd, 1H, pyridine), 9.55(s, 1H, NH).                      264  δ: 0.8-1.9(br s, 25H, aliphatic), 3.85-3.90(s, 6H, OCH.sub.3),          6.15(s, 1H, ArH, pyrimidine), 7.4(s, 2H, ArH).                           277  δ: 0.90(t, 3H, CH.sub.3), 1.2-1.7(m, 4H, aliphatic), 3.95(s,            6H, OCH.sub.3), 4.08(t, 2H, OCH.sub.2), 6.15(s, 1H,                           pyrimidine H), 7.5-7.7(m, 3H, aromatic).                                 281  δ: 0.90(t, 3H, CH.sub.3), 1.3(m, 4H, aliphatic), 1.6(s, 2H,             aliphatic), 3.95(s, 6H, OCH.sub.3), 4.08(t, 2H, OCH.sub.2),                   6.15(s, 1H, pyrimidine H), 7.4-7.7(s, 3H, aromatic).                     283  δ: 3.40(s, 6H, OCH.sub.3), 3.43(s, 2H, NCH.sub.2), 3.82(s, 6H,          OCH.sub.3), 4.47(t, 1H, CH), 5.75(s, 1H, OH),                                 5.86(s, 1H, pyrimidine), 6.77(s, 1H, OCH), 7.41(dd, 1H, pyridine),            7.96(dd, 1H, pyridine), 8.47(m, 2H, NH, pyridine).                       284  δ: 1.75(s, 6H, CH.sub.3), 2.31(s, 1H, C═CH), 3.85(s, 6H,            OCH.sub.3), 5.62(d, 1H, OH), 5.85(s, 1H, pyrimidine),                         6.85(d, 1H, OCH), 7.45(dd, 1H, pyridine), 7.95(dd, 1H, pyridine),             8.44-8.45(s, 2H, NH, pyridine).                                          285  δ: 0.85(t, 3H, CH.sub.3), 1.48(m, 4H, CH.sub.2), 3.41(m, 2H,            NCH.sub.2), 3.82(s, 6H, OCH.sub.3), 5.75(m, 2H, OH,                           pyrimidine), 6.66(d, 1H, OCH), 7.31(dd, 1H, pyridine), 7.86(d, 1H,            pyridine), 8.27(s, 1H, NH) 8.40(dd, 1H, pyridine).                       286  δ: 1.28(t, 3H, CH.sub.3), 3.38-3.58(m, 4H, CH, CH.sub.3),               3.85(s, 6H, OCH.sub.3), 4.18-4,48(s, 2H, CH.sub.2),                           5.88(s, 1H, pyrimidine), 6.73(3, 1H, OCH), 7.53-8.42(s, 4H,                   pyridine, NH).                                                           290  δ: 3.74(s, 9H, OCH.sub.3), 5.44(bs, 1H, OH), 5.73(s, 1H,                pyrimidine), 6.62(bs, 1H, OCH), 6.9-8.6(m, aromatic,                          7H), 10.22(s, 1H, NH).                                                   291  δ: 1.40(m, 8H, CH.sub.2), 2.28(s, 6H, NCH.sub. 3), 2.68(m, 2H,          NCH.sub.2), 3.40(m, 2H, NCH.sub.2), 3.80(s, 6H,                               OCH.sub.3), 5.80(s, 1H, pyrimidine), 6.70(s, 1H, OCH), 7.2-8.6(m,             4H, pyridine H + OH).                                                    292  δ: 1.60(m, 4H, CH.sub.2), 2.25(s, 6H, NCH.sub.3), 2.25(m, 2H,           NCH.sub.2), 3.48(m, 2H, NCH.sub.2), 3.65(s,                                   6H, OCH.sub.3), 5.80(s, 1H, pyrimidine), 6.65(s, 1H, OCH),                    7.2-8.6(m, 4H, pyridine + OH).                                           295  δ: 3.74(s, 6H, OCH.sub.3), 3.80(s, 6H, OCH.sub.3), 4.50(d, 2H,          NCH.sub.2), 5.84(s, 1H, pyrimidine), 6.5-8.6(m, 8H,                           phenyl, OCH, NH).                                                        297  δ: 3.65(s, 6H, OCH.sub.3), 3.77(s, 6H, OCH.sub.3), 4.50(d, 2H,          NCH.sub.2), 5.64(d, 1H, OH), 5.80(s, 1H, pyrimidine),                         6.25-6.60(m, 3H, phenyl), 6.8(d, 1H, OCH), 7.2-8.6(m, 3H,                     pyridine).                                                               298  δ: 1.21(d, 3H, CH.sub.3), 3.26(m, 1H, CH), 3.61(m, 2H,                  CH.sub.2), 3.82(s, 6H, OCH.sub.3), 5.86(s, 1H, pyrimidine), 6.7(s,            1H, CH), 7.38(dd, 1H, pyridine), 7.90(dd, 1H, pyridine), 8.43(dd,             1H, pyridine), 8.61(br, 1H, NH).                                         299  δ: 0.85(t, 3H, CH.sub.3), 1.2(m, 8H, aliphatic), 1.6(s, 2H,             aliphatic), 3.95(s, 6H, OCH.sub.3), 4.08(t, 2H,                               OCH.sub.2), 6.15(s, 1H, pyrimidine H), 7.4-7.7(m, 3H, aromatic).         300  δ: 0.90(t, 3H, CH.sub.3), 1.2(s, 10H, aliphatic), 1.6(m, 2H,            aliphatic), 3.95(s, 6H, OCH.sub.3), 4.08(t, 2H,                               OCH.sub.3), 4.08(t, 2H, OCH.sub.2), 6.15(s, 1H, pyrimidine H),                7.4-7.7(m, 3H, phenyl).                                                  303  δ: 3.80(s, 6H, OCH.sub.3), 3.90(d, 6H, OCH.sub.3), 5.45(d, 1H,          OH), 5.80(s, 1H, pyrimidine), 6.85(s, 1H, OCH),                               7.0-8.6(s, 6H, phenyl), 10.2(s, 1H, NH).                                 305L(-)                                                                            δ: 1.60(d, 3H, CH.sub.3), 3.75(2s, 6H, OCH.sub.3), 5.25(m, 1H,          OH), 5.75(s, 1H, pyrimidine),                                                 6.75(d, 1H, OCH), 7.2-8.6(m, 8H, aromatic).                              308  δ: 0.88(t, 3H, CH.sub.3), 1.25(bs, 18H, aliphatic), 1.6(s, 2H,          aliphatic), 3.95(s, 6H, OCH.sub.3),                                           4.07(t, 2H, O--CH.sub.2), 6.15(s, 1H, pyrimidine H), 7.55-7.7(m, 3H,          aromatic).                                                               330  δ: 1.05(m, 6H, NCH.sub.2 CH.sub.3), 1.27(s, 9H,                         C(CH.sub.3).sub.2), 2.3(m, 4H, NCH.sub.2), 3.8(s, 6H,                         OCH.sub.3), 5.8(s, 1H, pyrimidine H), 5.9(s, 1H, CH--Ot--Bu), 7.18(d          of d, 1H, pyridine H), 7.45(d of d, 1H,                                       pyridine H), 8.6(d of d, 1H, pyridine H).                                393  δ: 0.86(d, 3H, CH.sub.3), 1.12-1.26(m, 8H, CH.sub.2), 3.15(s,           3H, NCH.sub.3), 3.32(m, 2H, CH.sub.2), 3.93(s,                                6H, OCH.sub.3), 6.14(s, 1H, pyrimidine), 7.46(dd, Jca=4.8, Jcb=7.8,           1H, pyridine), 8.12(dd, Jba=1.3, Jbc=7.8, 1H,                                 pyridine), 8.68(dd, Jab=1.2, Jac=4.8).                                   395  δ: 3.10(s, 3H, N--CH.sub.3), 3.86(s, 6H, OCH.sub.3), 4.58(s,            2H, CH.sub.2), 6.06(s, 1H, pyrimidine), 7.18-8.69(m, 8H,                      pyridine, phenyl).                                                       407  δ: 3.18(m, 2H, CH.sub.2 S), 3.65(s, 2H, CH.sub.2 N), 3.95(s,            6H, OCH.sub.3), 5.85(s, 1H, pyrimidine), 6.80(s, 1H, OCH),                    7.0-8.7(s, 8H, aromatic).                                                411  δ: 1.90(t, 3H, CH.sub.3), 1.55(s, 4H, CH.sub.2), 2.65(s, 4H,            CH.sub.2 S), 3.62(m, 2H, CH.sub.2 N), 3.82(s, 6H, CH.sub.3 O),                5.90(s, 1H, pyrimidine), 6.75(s, OCH), 7.2-8.65(m, 3H, pyridine).        412  δ: 1.37(s, 9H, tBuO), 3.30(s, 3H, CH.sub.3 N), 3.90(s, 6H,              CH.sub.3), 5.95(s, 1H, pyrimidine), 5.97(s, 1H, OCH), 6.5-7.6(m,              10H, aromatic).                                                          413  δ: 2.23(s, 1H, C.tbd.CH), 3.12-3.23(d, 3H, N-CH.sub.3),                 3.93(s, 8H, OCH.sub.3, N--CH.sub.2 C.tbd.), 6.15(s, 1H,                       pyrimidine),                                                                  7.47-7.52(m, 1H, pyridine), 8.14-8.17(m, 1H, pyridine), 8.69-8.71(t,          1H, pyridine).                                                           428  δ: 0.71-1.80(m, 8H, alphatic), 3.02(s, 6H, OCH.sub.3),                  3.92-4.20(m, 1H, NCH), 5.82(s, 1H, pyrimidine), 6.67(s, 1H, OCH),             7.20-8.50(m, 4H, pyridine + NH).                                         429  δ: 3.38(s, 3H, NCH.sub.3), 4.02(s, 6H, OCH.sub.3), 6.20(s, 1H,          pyrimidine), 6.63-7.90(m, 10H, aromatic).                                430  δ: 1.3(s, 9H, t-Bu), 3.4(s, 3H, N--CH.sub.3), 3.9(s, 6H,                OCH.sub.3), 5.9(s, H, pyrimidine H), 6.57(s, 2H, CH--O +                      thiophene H), 7.05(m, 6H, thiophene H, phenyl).                          431  δ: 3.46(s, 3H, N--CH.sub.3), 3.97(s, 6H, OCH.sub.3), 5.2(d,             1H, OH), 5.87(s, 1H, pyrimidine H), 6.1(d, 1H, CH--O),                        6.32(d, 1H, thiophene H), 6.75(d, 1H, thiophene H), 7.05(m, 5H,               phenyl).                                                                 432  δ: 0.92(t, 3H, CH.sub.3), 1.42(m, 6H, CH.sub.2), 3.42(m, 2H,            NCH.sub.2), 3.85(s, 6H, OCH.sub.3), 5.85(9, 1H, pyrimidine),                  6.72(d, 1H, OCH), 7.22-9.60(m, 4H, pyridine + NH).                       433  δ: 0.90(t, 3H, CH.sub.3), 1.32(s, 10H, CH), 3.45(m, 2H,                 NCH.sub.2), 3.92(s, 6H, OCH.sub.3), 5.85(s, 1H, pyrimidine),                  6.75(s, 1H, OCH), 7.2-8.6(m, 4H, pyridine + NH).                         435  δ: 0.96(t, 3H, CH.sub.3), 1.92(m, 2H, CH.sub.2), 3.78(s, 3H,            OCH.sub.3), 3.86(s, 1H, OCH.sub.3), 4.60(m, 1H, NCH),                         5.86(s, 1H, pyrimidine), 6.86(d, 1H, OCH), 7.2-8.9(m, 4H, pyridine +          NH).                                                                     436  (S)-(+)-amine δ: 0.76-1.74(s, 8H, CH.sub.3, CH.sub.2), 3.86(s,          6H, OCH.sub.3), 4.06(m, 1H, NCH), 5.86(s, 1H, pyrimidine),                    6.70(d, 1H, OCH), 7.60-8.60 (m, 4H, pyridine, NH).                       436  (R)-(-)-amine δ: 0.70-1.85(m, 8H, CH.sub.3, CH.sub.2), 3.90(s,          6H, OCH.sub.3), 4.05(m, 1H, NCH), 5.85(s, 1H, pyrimidine),                    6.65(s, 1H, OCH), 7.20-8.60(m, 4H, pyridine, NH).                        437  δ: 2.25(m, 1H, .tbd.CH), 2.45(s, 3H, CH.sub.3), 3.80(s, 3H,             OCH.sub.3), 4.25(m, 2H, NCH.sub.2), 6.38(s, 1H, pyrimidine),                  6.95(s,                                                                       1H, OCH), 7.25-8.65(m, 4H, pyrimidine, NH).                              446  δ: 1.45(t, 3H, CH.sub.3), 3.82(s, 6H, OCH.sub.3), 4.12(q, 2H,           OCH.sub.2), 5.42(d, 1H, OH), 5.88(s, 1H, pyrimidine), 6.72(m, 1H,             OCH), 7.00-8.65(m, 7H, phenyl, pyridine), 10.32(s, 1H, NH).              448  δ: 3.45(s, 3H, NCH.sub.3), 3.95(s, 6H, OCH.sub.3), 5.35(s, 1H,          OH), 5.95(s, 1H, pyrimidine), 6.15(s, 1H, OCH), 6.90-740(m, 5H,               phenyl), 7.94(s, 1H, isothiazole).                                       450  δ: 3.38(s, 3H, NCH.sub.3), 3.72(s, 6H, OCH.sub.3), 4.47(s, 2H,          CH.sub.2), 5.38(s, 1H, OH), 6.94-8.62(m, 8H, OCH, benzene,                    pyridine),                                                                    10.64(s, 1H, NH).                                                        458  δ: 3.10(s, 3H, N--CH.sub.3), 3.95(m, 8H, CH.sub.2, OCH.sub.3),          5.19(m, 1H, ═CH), 6.17(s, 1H, pyrimidine), 7.49(dd, 1H                    pyridine),                                                                    8.16(dd, 1H, pyridine), 8.69(dd, 1H, pyridine).                          462  δ: 3.40(s, 3H, OCH.sub.3), 3.82(s, 6H, OCH.sub.3), 4.48(s, 2H,          CH.sub.2), 4.63(d, 2H, NCH.sub.2), 5.73(d, 1H, OH), 5.88(s, 1H,               pyrimidine), 6.80(d, 1H, OCH), 7.28-8.80(s, 8H, benzene, pyridine,            NH).                                                                     463  δ: 3.83(s, 6H, OCH.sub.3), 4.43(d, 1H, OH), 5.75(s, 1H,                 pyrimidine), 6.75(s, 1H, OCH), 7.10-8.45(m, 7H, phenyl,                       pyridine), 8.70(t, 1H, NH).                                              469  δ: 3.80(s, 6H, OCH.sub.3), 3.90(d, 6H, OCH.sub.3), 5.60(d, 1H,          OH), 5.85(s, 1H, pyrimidine), 6.35-8.70(m, 7H, OCH, pyridine,                 phenyl),                                                                      10.30(s, 1H, NH).                                                        470  δ: 1.10(t, 6H, CH.sub.3), 2.53(q, 4H, CH.sub.2), 3.75(s, 6H,            OCH.sub.3), 5.80(s, 1H, pyrimidine), 5.90(d, 1H, OH), 6.45(d, 1H,             OCH),                                                                         7.00-8.60(m, 6H, phenyl, pyridine), 9.78(s, 1H, NH).                     471  δ: 3.34(s, 3H, OCH.sub.3), 3.37(s, 6H, OCH.sub.3), 4.42(s, 2H,          OCH.sub.2), 4.63(d, 2H, NCH.sub.2), 5.74(d, 1H, OH), 5.80(s, 1H,              pyrimidine), 6.80(d, 1H, OCH), 7.22-8.50(M, 7H, phenyl, pyrimidine),          8.65(t, 1H, NH).                                                         473  δ: 3.35(s, 3H, N--CH.sub.3), 3.95(s, 6H, OCH.sub.3), 6.27(s,            1H, CH), 6.66(s, 1H, pyrimidine), 6.93-9.93(d, 8H,                            phenyl, pyridine).                                                       475  δ: 3.40(s, 3H, OCH.sub.3), 3.75(s, 6H, OCH.sub.3), 4.52(s, 2H,          CH.sub.2), 4.66(d, 2H, NCH.sub.2), 5.82(d, 1H, OH), 5.85(s,                   1H, pyrimidine), 6.76(d, 1H, OCH), 7.20-8.60(s, 7H, phenyl,                   pyridine), 8.85(t, 1H, NH).                                              482  δ: 2.20-2.70(s, 10H, NCH.sub.2, CH.sub.2), 3.40-3.80(m, 4H,             OCH.sub.2), 3.85(s, 6H, OCH.sub.3), 5.85(s, 1H, pyrimidine), 6.20(s,          1H,                                                                           OCH), 7.15-8.70(m, 3H, pyridine).                                        483  δ: 0.60-1.80(m, 11H, CH.sub.2, CH.sub.3), 2.60-3.00(m, 2H,              NCH.sub.2), 3.88(s, 6H, OCH.sub.3), 5.85(s, 1H, pyrimidine), 6.20(s,          1H, OCH),                                                                     7.00-8.70(m, 3H, pyridine).                                              490  δ: 2.55(t, 1H, .tbd.CH), 3.82(s, 6H, OCH.sub.3), 4.68(d, 1H,            OCH.sub.2), 5.45(d, 1H, OH), 5.85(s, 1H, pyrimidine), 6.90(d,                 1H, OCH), 6.90-8.70(m, 7H, phenyl, pyridine), 10.25(s, 1H, NH).          491  δ: 2.55(t, 1H, .tbd.CH), 3.80(9, 6H, OCH.sub.3), 5.42(d, 1H,            OH), 5.84(s, 1H, pyrimidine), 6.90(m, 1H, OCH), 6.80-8.70(m, 7H,              phenyl, pyridine), 10.40(s, 1H, NH).                                     496  δ 3.19(s, 3H, N--CH.sub.3), 3.69(t, 2H, CH.sub.2), 3.82(s, 2H,          CH.sub.2), 3.94(s, 6H, OCH.sub.3), 6.17(s, 1H, pyrimidine),                   7.55(dd, 1H, pyridine), 8.19(dd, 1H, pyridine), 8.61(dd, 1H,                  pyridine).                                                               497  δ: 0.89(t, 3H, CH.sub.3), 1.26(m, 4H, CH.sub.2), 3.14(s, 3H,            --NCH.sub.3), 3.34(m, 2H, CH.sub.2), 3.93(s, 6H, OCH.sub.3),                  6.15(s, 1H, pyrimidine), 7.46(dd, 1H, pyridine), 8.13(dd, 1H,                 pyridine), 8.68(dd, 1H, pyridine).                                       498  δ: 0.70-1.70(m, 10H, CH.sub.2, CH.sub.3), 3.85(s, 6H,                   OCH.sub.3), 4.20(m, 1H, NCH), 5.85(s, 1H, pyrimidine),                        5.95(d, 1H, OH), 6.68(d, 1H, OCH), 7.25-8.65(m, 4H, pyridine, NH).       500  δ: 2.30(s, 6H, N(CH.sub.3)2), 3.19(s, 3H, N--CH.sub.3),                 3.54(m, 4H, CH.sub.2), 3.94(s, 6H, OCH.sub.3),                                6.16(s, 1H, pyrimidine), 7.48(dd, Jca= 2.8, Jcb=4.8, 1H, pyridine),           8.15(dd, Jbc=4.8, Jba=1.5, 1H, pyridine),                                     8.69(dd, Jca=2.8, Jab=1.5, 1H, pyridine).                                501  δ: 3.16(s, 3H, NCH.sub.3), 3.19-3.27(m, 9H, OCH.sub.3,                  CH.sub.2, CH), 3.71(s, 6H, OCH.sub.3),                                        5.96(s, 1H, pyrimidine), 7.27-7.31(d, 1H, pyridine), 7.93-7.96(d,             1H, pyridine), 8.46-8.50(d, 1H, pyridine).                               505  δ: 3.35-4.10(m, 6H, NCH.sub.2, OCH.sub.2, NH, OH), 3.80(s, 6H,          OCH.sub.3) 5.75(d, 1H, OH), 5.80(s, 1H,                                       pyrimidine), 6.70(d, 1H, OCH), 7.20-8.50(m, 3H, pyridine), 8.60(s,            1H, NH).                                                                 506  δ: 1.00(m, 6H, CH.sub.3), 1.60(m, 3H, CH.sub.2, CH),                    3.75-4.38(m, 6H, NH, NCH, CH.sub.2 OH),                                       3.88(s, 6H, OCH.sub.3), 5.90(s, 1H, pyrimidine), 6.76(s, 1H, OCH),            7.28-8.72(m, 4H, pyridine, NH).                                          508  δ: 3.27(s, 3H, NCH.sub.3), 3.53(d, 2H, CH.sub.2), 3.61(t, 1H,           CH), 3.82(m, 4H, CH), 3.87(s, 6H,                                             OCH.sub.3), 6.16(s, 1H, pyrimidine), 7.48(dd, 1H, pyridine),                  8.14(dd, 1H, pyridine), 8.69(dd,                                              1H, pyridine).                                                           509  δ: 3.25(s, 3H, NCH.sub.3), 3.67(t, 2H, CH.sub.2), 3.71(t, 2H,           CH.sub.2), 3.94(s, 6H,                                                        OCH.sub.3), 6.19(s, 1H, pyrimidine), 7.50(dd, Jca=4.8, Jcb=7.8, 1H,           pyridine), 8.18(dd, Jba=1.5,                                                  Jbc=7.8, 1H, pyridine), 8.72(dd, Jab=1.5, Jac=4.8, 1H, pyridine).        510  δ: 1.77(s, 3H, CH.sub.3), 3.80(s, 6H, OCH.sub.3), 3.98(d, 2H,           N--CH.sub.2), 4.90(s, 2H, ═CH.sub.2),                                     5.70(d, 1H, OH), 5.85(s, 1H, pyrimidine), 6.8(d, 1H, OCH),                    7.2-7.5(m, 1H, pyridine), 7.8-8.05(d, 1H, pyridine),                          8.4-8.6(d, 1H, pyridine).                                                511  δ: 0.18(s, 9H, Si(CH.sub.3).sub.3), 3.47(s, 3H, N--CH.sub.3),           3.90(s, 6H, OCH.sub.3), 4.20(s, 2H,                                           CH.sub.2), 5.88(s, 1H, pyrimidine C--H), 7.04(s, 1H, thiophene                C--H), 7.17(s, 5H, phenyl).                                              512  δ: 0.12(s, 9H, Si(CH.sub.3).sub.3), 1.24(s, 9H, O-t-Bu),                3.38(s, 3H, N--CH.sub.3), 3.84(s, 6H,                                         OCH.sub.3), 5.83(s, 1H, pyrimidine C--H), 6.20(s, 1H, CH--O),                 7.05(s, 5H, phenyl),                                                          7.37(s, 1H, thiophene, C--H).                                            513  δ: 0.75-1.15(t, 3H, CH.sub.3), 1.15-1.70(m, 6H, CH.sub.2),              2.25-2.70(m, 2H, OCH, OH), 3.45-4.00(m,                                       2H, NCH.sub.2), 3.85(s, 6H, OCH.sub.3), 5.85(s, 1H, pyrimidine),              6.80(s, 1H, OCH), 7.30-8.80(m, 4H,                                            pyridine, NH).                                                           514  δ : 0.90(t, 3H, CH.sub.3), 1.10-1.67(m, 9H, CH.sub.2,                   CH.sub.3), 3.85(s, 6H, OCH.sub.3), 4.10(s, 1H, NCH),                          5.90(s, 1H, pyrimidine), 5.94(d, 1H, OH), 6.80(d, 1H, OCH),                   7.28-8.66(m, 4H, pyridine, NH).                                          515  δ: 1.606(m, 3H, CH.sub.3), 2.30(m, 1H, .tbd.CH), 3.90(s, 6H,            OCH.sub.3), 3.92(m, 1H, NCH), 5.85(s,                                         1H, pyrimidine), 5.95(s, 1H, OH), 6.95(s, 1H, OCH), 7.20-8.70(m, 4H,          pyridine, NH).                                                           516  δ: 0.95(t, 3H, CH.sub.3), 1.50(q, 2H, CH.sub.2), 3.62(m, 2H,            NCH.sub.2), 3.85(s, 6H, OCH.sub.3), 3.87(m,                                   1H, OCH), 5.35(d, 1H, OH), 5.85(s, 1H, pyrimidine), 6.75(d, 1H,               OCH), 7.30-8.80(m, 4H, pyridine, NH).                                    517  δ: 1.00-2.25(m, 10H, CH.sub.2), 3.85(s, 6H, OCH.sub.3),                 3.98(s, 1H, NCH), 5.85(s, 1H, pyrimidine), 5.88(d, 1H, OH), 6.68(d,           1H, OCH), 7.20-8.60(m, 4H, pyridine, NH).                                518  δ: 3.78(s, 6H, OCH.sub.3), 6.40(s, 1H, pyrimidine), 7.78(dd,            Jca=4.7, Jcb=7.7, 1H, pyridine), 8.17(dd, Jbc=7.6,                            Jba=1.5, 1H, pyridine), 8.91(dd, Jac=4.7, Jab=1.5, 1H, pyridine).        519  δ: 2.12(m, 2H, CH.sub.2), 3.44(m, 2H, NCH.sub.2), 3.84(s, 6H,           OCH.sub.3), 4.00(m, 2H, NCH.sub. 2), 4.87(s,                                  1H, OH), 5.85(s, 1H, pyrimidine), 6.77(s, 1H, OCH), 6.90-8.68(m, 7H,          pyridine, imidazole, NH).                                                523  δ: 1.33(t, 3H, CH.sub.3), 3.85(s, 6H, OCH.sub.3), 4.14(s, 2H,           CH.sub.2), 4.40(q, 2H, OCH.sub.2), 5.87(s, 1H, pyrimidine H),                 7.35(d, 1H, pyridine H), 8.33(d, 1H, pyridine H).                        530  δ: 0.50(s, 9H, Si(CH.sub.3).sub.3), 3.40(s, 3H, NCH.sub.3),             3.85(s, 6H, OCH.sub.3), 4.10(s, 2H, CH.sub.2), 5.83(s, 1H,                    pyrimidine),                                                                  7.00-7.40(m, 5H, benzene).                                               532  δ: 3.01-3.50(m, 2H, CH.sub.2 OH), 3.59-3.61(s, 4H, OCH.sub.2),          3.71-3.73(2, 2H, CH.sub.2 N), 3.99(s, 6H, OCH.sub.3), 5.76(br s,              3H, NH), 6.08(s, 1H, pyrimidine), 7.27-7.31(m, 1H, aromatic),                 7.45-7.51(s, 2H, aromatic).                                              553  δ: 1.41-1.46(t, 3H, CH.sub.3), 3.89(s, 6H, OCH.sub.3),                  4.47-4.52(q, 2H, OCH.sub.2), 5.93(s, 1H, CHBr), 6.52(s, 1H,                   pyrimidine),                                                                  8.35(d, 1H, J=5.25 Hz, pyridine), 8.83(s, 1H, J=5.25 Hz, pyridine).      562  δ: 2.5(s, 3H, CH.sub.3), 3.9(s, 6H, OCH.sub.3), 5.9(s, 1H,              CHOH), 6.2(s, 1H, pyrimidine), 7.3(d, 1H, J=12 Hz, pyridine),                 8.3(d,                                                                        1H, J=12 Hz, pyridine).                                                  571  δ: 1.26(t, 3H, CH.sub.3), 3.33(s, 3H, NCH.sub.3), 3.94(s, 6H,           OCH.sub.3), 4.11(s, 2H, NCH.sub.2), 4.25(q, 2H,                               OCH.sub.2), 6.15(s, 1H, pyrimidine), 7.51(dd, Jca=4.8, ;Jcb=7.6, 1H,          pyridine), 8.10(dd, Jbc=7.7, Jab=1.6, 1H, pyrimidine),                        8.65(dd, Jac=4.8, Jab=1.6, 1H, pyridine).                                622  δ: 0.84(t, 3H, CH.sub.3), 1.08(d, 3H, CH.sub.3), 1.56(m, 2H,            CH.sub.2), 3.89(s, 6H, OCH.sub.3), 4.78(m, 1H, CH), 6.13(s,                   1H, pyrimidine), 7.62(dd, Jca=4.8, Jcb=7.6, 1H, pyridine), 7.94(dd,           Jba=1.6, Jbc=7.6, 1H, pyridine), 8.85(dd, Jab=1.6,                            Jac=4.8, 1H, pyridine).                                                  625  δ: 0.87(t, 3H, CH.sub.3), 1.28(m, 2H, CH.sub.2), 1.54(m, 2H,            CH.sub.2),                                                                    3.89(s, 6H, OCH.sub.3), 4.09(t, 2H, OCH.sub.2), 6.13(s, 1H,                   pyrimidine), 7.62(dd, Jca=4.7, Jcb=7.7, 1H, pyridine), 7.99(dd,               Jba=1.5, Jbc=7.7, 1H, pyridine), 8.84(dd, Jab=1.5, Jac=4.17, 1H,              pyridine).                                                               __________________________________________________________________________

What is claimed is:
 1. A compound of formula I ##STR349## wherein R is acarboxyl group which may be in the form of the free acid or in ester orsalt form, a thiocarboxyl group which may be in the form of the freeacid or in ester form, a carbamoyl group or a mono- or di- substitutedcarbamoyl group,Y₁, Y₂ and Y₃ are independently hydrogen, halogen,hydroxy, alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy,alkylsulfonyloxy, dialkylsulfamoyloxy, alkylsulfonyl, alkylsulfinyl,dialkylcarbamoyloxy, alkylthio, alkenylthio or alkynylthio each of whichmay in turn be substituted by 1 to 6 halogen atoms; dialkoxymethyl,conjugated alkoxy, hydroxyalkyl, carboxyl, acyl, acylalkyl, acyloxy,acyloxyalkyl, trialkylsilyloxy, trialkylsilyl, cyano, nitro, amino orsubstituted amino, aminosulfonyl; cycloalkyl, aryl, aralkyl, aralkenyl,aralkynyl, aryloxy, aralkoxy, arylsulfonyl, arylsulfinyl, arylthio oraralkylthio, each of which may be substituted by one to threesubstituents selected from halogen, alkyl, haloalkyl, alkoxy,haloalkoxy, nitro, cyano, alkylthio, acyl, amino or substituted amino; agroup ##STR350## wherein R' is hydrogen, lower alkyl, or lower alkoxy;or Y₁ and R taken together on adjacent carbon atoms form a bridge havingthe formula ##STR351## wherein E is a 1 to 3 membered linking group withelements selected from methylene, substituted methylene, ##STR352## andoxygen, and each R₂ is independently hydrogen, hydroxy, alkyl,haloalkyl, alkoxy, alkoxyalkyl, aralkoxy, or aryl or aralkyl, each ofwhich is unsubstituted or may be substituted by 1 to 3 substituentsselected from halogen; alkyl, alkenyl, alkynyl, alkoxy, alkoxyalkoxy,alkenyloxy, alkynyloxy, alkylsulfonyl, alkylsulfinyl, alkylthio,alkenylthio or alkynylthio, nitro, cyano, acyl, amino; or Y₁ and Y₂taken together on adjacent carbon atoms form a 3- to 5-membered bridgecomprised of elements selected from methylene, substituted methylene,##STR353## R₁, R₃, and R'₃ each is independently hydrogen; halogen;alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio,alkenylthio or alkynylthio, each of which may in turn be substituted by1 to 6 halogen atoms; cycloalkyl, heterocycloalkoxy, aryloxy, aralkoxyor aralkylthio each of which may be substituted by 1 to 3 substituentsselected from halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, nitro,cyano, alkylthio, acyl, amino or substituted amino; aminoxy; substitutedaminoxy; iminoxy; substituted iminoxy; amino; substituted amino; amido;substituted amido; alkylsulfonylmethyl; cyano; nitro; or ##STR354##wherein Y₄ is hydrogen, lower alkyl, lower alkoxy, hydroxy orunsubstituted or substituted phenyl; R₄ is as deemed for Y₁ except forhydrogen; X and Y taken together represent ═O; or X and R taken togethermay form the bridge, ##STR355## wherein the carbonyl is attached to thephenyl ring, and Y is hydroxy, halogen, cyano, acyloxy, amino,substituted amino, alkoxycarbonyloxy, alkylsulfonyloxy, or carbamoyloxy.2. A compound according to claim 1 wherein Y₁, Y₂ and Y₃ areindependently hydrogen, halogen, hydroxy, alkyl, alkenyl, alkynyl,alkoxy, alkenyloxy, alkynyloxy, alkylsulfonyloxy, dialkylsulfamoyloxy,alkylsulfonyl, alkylsulfinyl, dialkylarbamoyloxy, alkylthio, alkenylthioor alkynylthio each of which may in turn be substituted by 1 to 6halogen atoms; dialkoxymethyl, conjugated alkoxy, hydroxyalkyl, acyl,acyloxy, trialkylsilyloxy, trialkylsilyl, cyano, nitro, amino orsubstituted amino, aryl, aralkyl, aryloxy, aralkoxy, arylsulfonyl,arylsulfinyl, arylthio or aralkylthio, each of which may be substitutedby one to three substituents selected from halogen, alkyl, haloalkyl,alkoxy, haloalkoxy, nitro, cyano, alkylthio, acyl, amino or substitutedamino; a group ##STR356## wherein R' is hydrogen, lower alkyl, or loweralkoxy; or Y₁ and R taken together on adjacent carbon atoms form abridge having the formula ##STR357## wherein E is a 1 to 3 memberedlinking group with elements selected from methylene, substitutedmethylene, ##STR358## and oxygen and each R₂ is independently hydrogen,alkyl, haloalkyl, alkoxyalkyl or aryl or aralkyl, each of which isunsubstituted or may be substituted by 1 to 3 substituents selected fromhalogen, alkyl, alkenyl, alkynyl, alkoxy, alkoxyalkoxy, alkenyloxy,alkynyloxy, alkylsulfonyl, alkylsulfinyl, alkylthio, alkenylthio,alkynylthio, nitro, cyano, acyl, amino or substituted amino; or Y₁ andY₂ taken together on adjacent carbon atoms form a 3- to 5-memberedbridge comprised of elements selected from methylene, substitutedmethylene, ##STR359##
 3. A compound according to claim 2 wherein Y₁, Y₂and Y₃ are independently hydrogen, halogen, alkyl, alkenyl, alkynyl,alkoxy, alkenyloxy, alkynyloxy, alkyl sulfonyloxy, dialkylsulfamoyloxy,alkylsulfonyl, alkylsulfinyl, dialkylcarbamoyloxy, alkylthio,alkenylthio or alkynylthio each of which may in turn be substituted by 1to 6 halogen atoms; dialkoxymethyl, alkoxyalkoxy, hydroxyalkyl, acyl,acyloxy, trialkylsilyloxy, trialkylsilyl, cyano, nitro, amino orsubstituted amino, aryl, aralkyl, aryloxy, aralkoxy, arylsulfonyl,arylsulfinyl, arylthio or aralkylthio, each of which may be substitutedby one to three substituents selected from halogen, alkyl, haloalkyl,alkoxy, haloalkoxy, nitro, cyano, alkylthio, acyl, amino or substitutedamino; a group ##STR360## wherein R' is hydrogen, lower alkyl, or loweralkoxy; or Y₁ and Y₂ taken together on adjacent carbon atoms form a 3-to 5-membered bridge comprised of elements selected from methylene,substituted methylene, ##STR361## Y₄ is hydrogen, lower alkyl, loweralkoxy or hydroxy; R₄ is as deemed for Y₁ except for hydrogen;X and Ytaken together represent ═O; or X and R taken together may form thebridge, ##STR362## wherein the carbonyl is attached to the phenyl ring,and Y is hydroxy, halogen, cyano, acyloxy, amino, substituted amino. 4.A compound according to claim 1 wherein Y₁, Y₂ and Y₃ are independentlyhydrogen, halogen, alkyl or alkoxy; R₁, R₃ and R₃ ' are independentlyhydrogen, halogen, alkyl, alkoxy, aryloxy, or aralkoxy.
 5. A compoundaccording to claim 2 wherein Y₁, Y₂ and Y₃ are independently hydrogen,halogen, alkyl or alkoxy; R₁, R₃ and R₃ ' are independently hydrogen,halogen, alkyl, alkoxy, aryloxy, or aralkoxy.
 6. A compound according toclaim 3 wherein Y₁, Y₂ and Y₃ are independently hydrogen, halogen, alkylor alkoxy; R₁, R₃ and R₃ ' are independently hydrogen, halogen, alkyl,alkoxy, aryloxy, or aralkoxy.
 7. A compound according to claim 1 whereinR represents carboxyl in the form of the free acid or in ester or saltform; substituted carbamoyl or, together with X represents ##STR363##Y₁, Y₂ and Y₃ are independently hydrogen, halogen, alkyl, alkoxy,alkylthio or arylthio;and R₁ and R₃ are independently halogen, alkyl,alkoxy, haloalkoxy, optionally substituted aryloxy, aralkoxy, alkynyloxyor alkenyloxy.
 8. A compound according to claim 2 wherein R representscarboxyl in the form of the free acid or in ester or salt form;substituted carbamoyl or, together with X represents ##STR364## Y₁, Y₂and Y₃ are independently hydrogen, halogen, alkyl, alkoxy, alkylthio orarylthio;and R₁ and R₃ are independently halogen, alkyl, alkoxy,haloalkoxy, optionally substituted aryloxy, aralkoxy, alkynyloxy oralkenyloxy.
 9. A compound according to claim 3 wherein R representscarboxyl in the form of the free acid or in ester or salt form;substituted carbamoyl or, together with X represents ##STR365## Y₁, Y₂and Y₃ are independently hydrogen, halogen, alkyl, alkoxy, alkylthio, orarylthioand R₁ and R₃ are independently halogen, alkyl, alkoxy,haloalkoxy, optionally substituted aryloxy, aralkoxy, alkynyloxy oralkenyloxy.
 10. A compound according to claim 1 wherein R is a carbamoylgroup or a mono- or di-substituted carbamoyl group.
 11. A compoundaccording to claim 2 wherein R is a carbamoyl group or a mono- ordi-substituted carbamoyl group.
 12. A compound according to claim 3wherein R is a carbamoyl group or a mono- or di-substituted carbamoylgroup.
 13. A compound according to claim 1 wherein Y₁, Y₂ and Y₃ areselected from the following meaningsa) independently hydrogen or halogenb) Y₁ and Y₂ independently halogen and Y₃ hydrogen c) Y₁ ortho to R aschlorine or fluorine, Y₂ ortho to the bridge as hydrogen, chlorine orfluorine, Y₃ hydrogen d) Y₁ ortho to R as chlorine, Y₂ ortho to thebridge as hydrogen, chlorine or fluorine, Y₃ hydrogen.
 14. A compoundaccording to claim 3 wherein Y₁, Y₂ and Y₃ are selected from thefollowing meaningsa) independently hydrogen or halogen b) Y₁ and Y₂independently halogen and Y₃ hydrogen c) Y₁ ortho to R as chlorine orfluorine, Y₂ ortho to the bridge as hydrogen, chlorine or fluorine, Y₃hydrogen d) Y₁ ortho to R as chlorine, Y₂ ortho to the bridge ashydrogen, chlorine or fluorine, Y₃ hydrogen.
 15. A compound according toclaim 3 wherein Y₁, Y₂ and Y₃ are selected from the following meaningsa)independently hydrogen or halogen b) Y₁ and Y₂ independently halogen andY₃ hydrogen c) Y₁ ortho to R as chlorine or fluorine, Y₂ ortho to thebridge as hydrogen, chlorine or fluorine, Y₃ hydrogen d) Y₁ ortho to Ras chlorine, Y₂ ortho to the bridge as hydrogen, chlorine or fluorine,Y₃ hydrogen.
 16. A compound according to claim 1 wherein R₃ ' ishydrogen and R₁ and R₃ are selected from the following meaningsa)independently lower alkoxy b) both methoxy.
 17. A compound according toclaim 2 wherein R₃ ' is hydrogen and R₁ and R₃ are selected from thefollowing meaningsa) independently lower alkoxy b) both methoxy.
 18. Acompound according to claim 3 wherein R₃ ' is hydrogen and R₁ and R₃ areselected from the following meaningsa) independently lower alkoxy b)both methoxy.
 19. A compound according to claim 1 wherein R is selectedfrom the following meaningsa) a carboxyl group which may be in the formof the free acid or in ester or salt form b) a carboxyl group in saltform.
 20. A compound according to claim 2 wherein R is selected from thefollowing meaningsa) a carboxyl group which may be in the form of thefree acid or in ester or salt form b) a carboxyl group in salt form. 21.A compound according to claim 3 wherein R is selected from the followingmeaningsa) a carboxyl group which may be in the form of the free acid orin ester or salt form b) a carboxyl group in salt form.
 22. A compoundaccording to claim 1 wherein R is a carboxyl group which may be in theform of the free acid or in ester or salt form;Y₁, Y₂ and Y₃ areindependently hydrogen or halogen; R₁, and R₃ are independently loweralkoxy; R₃ ' is hydrogen; X and Y together represent ═O or X and Rtogether form the bridge ##STR366## wherein the carbonyl is attached tothe phenyl ring and Y is hydroxy, halogen, cyano, acyloxy, amino,substituted amino, alkoxycarbonyloxy, alkylsulfonyloxy or carbamoyloxy.23. A compound according to claim 22 wherein X and Y together represent═O or X and R together form the bridge ##STR367## wherein the carbonylis attached to the phenyl ring and Y is hydroxy, halogen, cyano,acyloxy, amino or substituted amino.
 24. A compound according to claim11 which is4,7-dichloro-3-(4,6-dimethoxy-2-pyrimidinyl)-3-hydroxyphthalide.
 25. Acompound according to claim 1 which is3,6-dichloro-3-[(4,6-dimethoxy-2-pyrimidinyl)carbonyl]benzoic acidisopropylammonium salt.
 26. A compound according to claim 1 which is3,6-dichloro-3-[(4,6-dimethoxy-2-pyrimidinyl)carbonyl]benzoic acidsodium salt.
 27. A compound according to claim 1 which is4,7-dichloro-3-(4,6-dimethoxy-2-pyrimidinyl)-3-hexanoyloxyphthalide. 28.A compound according to claim 1 which is4,7-dichloro-3-(4,6-dimethoxy-2-pyrimidinyl)-3-butyryloxyphthalide. 29.A compound according to claim 11 which is6-chloro-2-[(4,6-dimethoxy-2-pyrimidinyl)carbonyl]-3-fluorobenzoic acidisopropyl ammonium salt.
 30. A herbicidal composition comprising aherbicidally effective amount of a compound according to claim
 11. 31. Aherbicidal composition comprising a herbicidally effective amount of acompound according to claim
 2. 32. A herbicidal composition comprising aherbicidally effective amount of a compound according to claim
 3. 33. Amethod of combatting weeds which comprises applying thereto or to alocus thereof an herbicidally effective amount of a compound accordingto claim
 1. 34. A method of combatting weeds which comprises applyingthereto or to a locus thereof an herbicidally effective amount of acompound according to claim
 2. 35. A method of combatting weeds whichcomprises applying thereto or to a locus thereof an herbicidallyeffective amount of a compound according to claim 3.